Process for making angstrom scale and high aspect functional platelets

ABSTRACT

A process for making functional or decorative flakes or platelets economically and at high production rates comprises applying a multi-layer sandwich of vapor deposited metal and release coats in alternating layers to a rotating chilled drum or suitable carrier medium contained in a vapor deposition chamber. The alternating metallized layers are applied by vapor deposition and the intervening release layers are preferably solvent soluble thermoplastic polymeric materials applied by vapor deposition sources contained in the vapor deposition chamber. The multi-layer sandwich built up in the vacuum chamber is removed from the drum or carrier and treated with a suitable organic solvent to dissolve the release coating from the metal in a stripping process that leaves the metal flakes essentially release coat free. The solvent and dissolved release material are then removed by centrifuging to produce a cake of concentrated flakes which can be air milled and let down in a preferred vehicle and further sized and homogenized for final use in inks, paints or coatings. In one embodiment the finished flakes comprise single-layer thin metal or metal alloy flakes or flakes of inorganic materials, and in another embodiment flakes are coated on both sides with protective polymeric coatings that were applied from suitable vacuum deposition sources or the like contained in the vapor deposition chamber.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application is a continuation-in-part of application Ser.No. 09/425,514, filed Oct. 22, 1999, which claims priority from U.S.Provisional Application No. 60/105,399, filed Oct. 23, 1998.

FIELD OF THE INVENTION

[0002] This invention relates to a process for producing angstrom scaleflakes or platelets that can be used for both functional and decorativeapplications. Some flakes produced by this process reach the nanoscalerange. The flakes can be metal, metal compounds, non-metal or clearflakes. Functional applications of the flakes include uses in protectivecoatings in which the flakes can add a level of rigidity to producecertain desired properties of the finished coating, or in which theflake layer can be used to screen out light of certain wave lengths toprotect an underlying pigmented layer. Reflective metal flakes areuseful in a variety of optical or decorative applications, includinginks, paints or coatings. Other uses of the flakes include microwave andelectrostatic applications, together with chemical process andbiological applications.

BACKGROUND

[0003] Conventional aluminum flake is manufactured in a ball millcontaining steel balls, aluminum metal, mineral spirits, and a fattyacid usually stearic or oleic. The steel balls flatten the aluminum andbreak it into flakes. When the ball milling is complete the slurry ispassed through a mesh screen for particle sizing. Flakes too large topass through the screen are returned to the ball mill for furtherprocessing. Flake of the proper size is passed through the screen andintroduced to a filter press where excess solvent is separated from theflake. The filter cake is then let down with additional solvent. Suchconventional aluminum flake typically has a particle size from about 2to about 200 microns and a particle thickness from about 0.1 to about2.0 microns. These flakes are characterized by high diffuse reflectance,low specular reflectance, rough irregular flake micro surface, and arelatively low aspect ratio.

[0004] Another process for making metal flakes is a process of AveryDennison Corporation for making flakes sold under the designationMetalure. In this process both sides of a polyester carrier are gravurecoated with a solvent-based resin solution. The dried coated web is thentransported to a metallizing facility where both sides of the coatedsheet are metallized by a thin film of vapor deposited aluminum. Thesheet with the thin metal film is then returned to the coating facilitywhere both sides of the aluminum are coated with a second film of thesolvent-based resin solution. The dried coated/metal sheet is thentransported again to the metallizing facility to apply a second film ofvapor deposited aluminum to both sides of the sheet. The resultingmulti-layer sheet is then transported for further processing to afacility where the coatings are stripped from the carrier in a solventsuch as acetone. The stripping operation breaks the continuous layerinto particles contained in a slurry. The solvent dissolves the polymerout from between the metal layers in the slurry. The slurry is thensubjected to sonic treatment and centrifuging to remove the solvent andthe dissolved coating, leaving a cake of concentrated aluminum flakesapproximately 65% solids. The cake is then let down in a suitablevehicle and further sized by homogenizing into flakes of controlled sizefor use in inks, paints, and coatings.

[0005] Metal flakes produced by this process for use in printableapplications such as inks are characterized by a particle size fromabout 4 to 12 microns and a thickness from about 150 to about 250angstroms. Coatings made from these flakes have a high specularreflectance and a low diffuse reflectance. The flakes have a smoothmirror-like surface and a high aspect ratio. The coatings also have ahigh level of coverage per pound of flake applied when compared withmetal flakes produced by other processes.

[0006] Flakes also are produced in a polymer/metal vacuum depositionprocess in which thin layers of vapor deposited aluminum are formed on athin plastic carrier sheet such as polyester or polypropylene, withintervening layers of cross-linked polymers between the vapor depositedaluminum layers. The cross-linked polymer layers are typically apolymerized acrylate deposited in the form of a vaporized acrylatemonomer. The multi-layer sheet material is ground into multi-layerflakes useful for their optical properties. Coatings produced from suchmulti-layer flakes tend to have a high diffuse reflectance and a lowspecular reflectance. The flakes have a low aspect ratio and undesiredlow opacity when made into an ink.

[0007] One objective of the present invention is to reduce the number ofmanufacturing steps and the resulting cost of making highly reflectivemetal flakes, although the process also reduces the coast of makingother flake-like materials described below.

[0008] In addition to metal flakes, there are many industrial uses ofglass (SiO₂) flakes. Conventional glass flakes generally have athickness range of about one to six microns and a diameter from about 30to about 100 microns. These glass flakes can be used for additions topolymers and coatings to improve various functional properties. Theseinclude addition of glass flakes as additives to produce thinner,smoother coatings, for example. One objective of this invention is toproduce very thin, flat, smooth flakes, such as metal or glass flakes,for example, for use of their various functional properties in polymers,coatings and films.

SUMMARY OF THE INVENTION

[0009] The present invention comprises a flake forming process in whicha multi-layer film is applied either to a thin, flexible polymericcarrier sheet such as polyester, or to a polished metal casting surfacesuch as a rotating metal drum. In either instance the process is carriedout in a vacuum deposition chamber. In one embodiment, the multi-layerfilm is applied to a polyester (PET) carrier sheet. The vacuum chamberis equipped with multiple deposition sources. The deposition sources canbe vaporization at elevated temperatures caused by heating by resistanceor EB. Air is evacuated from the chamber and the PET film is unwoundpast the coating and deposition sources while kept in contact with acooling drum. Alternating layers of materials can be applied to themoving PET web. One example is an organic solvent-soluble vapordeposited thermoplastic polymeric release material (having a depositionthickness of about 100 to about 400 angstroms), followed by a layer ofmetal such as aluminum (having a deposition thickness of about 5 toabout 500 angstroms), followed by another layer of the solvent-solublerelease material. Other metals, metal alloys, or inorganic compounds formaking glass flakes, for example, may be substituted for the aluminum.By reversing the web path and inactivating the second coating source andthen repeating the first step, many layers can be applied to the PETwithout breaking the vacuum, which can increase productivity. Additionalprotective layers can be deposited on each side of the metal layers byadding two additional deposition sources between the coating and metaldeposition sources. The multi-layered coated PET is introduced into anorganic solvent stripping process to remove the sandwich from the PET.The polymeric release coat material is dissolved by the organic solventto leave the deposited flake material essentially free of the releasematerial. The solvent is then centrifuged to produce a cake ofconcentrated flakes.

[0010] In an alternative embodiment, the same coating and depositiontechniques are used to apply alternating layers directly to a releasecoated cooling drum contained in the vacuum deposition chamber. The drumis rotated past the coating and deposition sources to build up amulti-layer sandwich of vapor deposited thermoplastic release materialand flake material in alternating layers. The multi-layer sheet is thenintroduced directly into an organic solvent with or without suitableagitation to produce flakes; or it can be ground to rough flakes whichcan also be air-milled to further reduce particle size, and thenintroduced into a solvent slurry to allow the remaining layers to beseparated. The solvent may be removed by centrifuging to produce a cakeof concentrated metal flakes, essentially free of any release material.The cake of concentrated flakes or the slurry of solvent and flakes thencan be let down in a preferred vehicle and further sized and homogenizedfor final use in inks, paints, plastics or coatings.

[0011] Another embodiment of the invention comprises a process formaking a release-coated heat-resistant polymeric carrier sheet in thevacuum deposition chamber. The carrier sheet can comprise a web ofpolyester (PET) as described above. The release coat comprises anorganic solvent soluable thermoplastic polymeric material vapordeposited on the polyester carrier. The release-coated carrier providesa flexible smooth surfaced carrier base upon which to vapor depositflake materials such as metal or glass to provide an effective releasesurface for making angstrom scale flakes. The flakes are exceedinglythin and flat when released from the thermoplastic release coat via asuitable organic solvent.

[0012] Other embodiments of the invention comprise techniques forcontrolling delivery of the vapor deposited thermoplastic polymericrelease coat material to the vacuum chamber. These include a rotatingdrum, heater block and E-beam embodiment; several embodiments comprise awire feed mechanism used to coat the polymer on a wire which is fed intothe vacuum chamber and heated to evaporate the polymer and deposit it ona rotating drum or other carrier surface.

[0013] Further embodiments comprise applications of the angstrom scaleparticles made by this invention which include flakes used to controlwater vapor transmission rates in barrier materials and electricalapplications in which the angstrom scale flakes can be used to produceconstructions having exceedingly high electrical capacitance.

[0014] These and other aspects of the invention will be more fullyunderstood by referring to the following detailed description and theaccompanying drawings.

DRAWINGS

[0015]FIG. 1 is a schematic functional block diagram illustrating aprior art process for manufacturing metal flakes.

[0016]FIG. 2 is a schematic elevational view illustrating a vacuumdeposition chamber for applying a multi-layer coating in a firstembodiment of a process according to this invention.

[0017]FIG. 3 is a schematic cross-sectional view illustrating a sequenceof layers in one embodiment of the multi-layer sheet material accordingto this invention.

[0018]FIG. 4 is a schematic cross-sectional view illustrating amulti-layer sheet material made according to another embodiment of thisinvention.

[0019]FIG. 5 is a functional block diagram schematically illustratingprocessing steps in the first embodiment of this invention.

[0020]FIG. 6 is a schematic cross-sectional view illustrating singlelayer flakes made by the process of this invention.

[0021]FIG. 7 is a schematic cross-sectional view of multi-layer flakesmade by the process of this invention.

[0022]FIG. 8 is a schematic elevational view illustrating a secondembodiment for producing the metal flakes of this invention.

[0023]FIG. 9 is a functional block diagram schematically illustratingprocessing steps for making flakes from the multi-layer material madeaccording to the second embodiment of the invention.

[0024]FIG. 10 is a semi-schematic elevational view illustrating a belljar vacuum chamber.

[0025]FIG. 11 is a semi-schematic side elevational view showing a vacuumchamber containing a rotating drum and heater block assembly.

[0026]FIG. 12 is a side elevational view of a rotating drum and heatedpolymer vapor chamber shown in FIG. 11.

[0027]FIG. 13 is a semi-schematic side elevational view showing vacuumchamber and heater block assembly similar to FIGS 11 and 12 incombination with a wire feed apparatus for delivering polymeric releasecoat material to a rotating drum surface in the vacuum chamber.

[0028]FIG. 14 is a side elevational view of the rotating drum and heaterblock assembly illustrated in FIG. 13.

[0029]FIG. 15 is one embodiment of a wire feed mechanism and vapor tubecombination for delivering polymer release coat material to a vacuumchamber.

[0030]FIG. 16 is a side elevational view of a heated polymer vapor tubeand rotating drum shown in FIG. 15.

[0031]FIGS. 15A and 16A are alternative embodiments of the wire feedmechanism shown in FIGS. 15 and 16;

[0032]FIG. 17 is a semi-schematic side elevational view illustrating aheated melt tube apparatus for delivering polymeric base coat materialto a vacuum chamber.

[0033]FIG. 18 is a side elevational view showing a heated polymer vaportube and rotating drum illustrated in FIG. 17.

[0034]FIG. 19 is a semi-schematic side elevational view illustrating aprocess for making carrier sheet material with a polymeric release coataccording to principles of this invention.

[0035]FIG. 20 is a semi-schematic elevational view showing a melt pumpprocess for delivering polymer release material to a vacuum chamber.

DETAILED DESCRIPTION

[0036] In order to better appreciate certain aspects of this invention,reference is made to FIG. 1 which illustrates a prior art process formaking metal flakes according to a process presently utilized by AveryDennison Corporation for manufacturing flakes sold under the designationMetalure. According to this prior art process, both sides of a polyestercarrier sheet 10 are gravure coated at 12 with a solvent-based resinsolution 14. The dried coated web is then transported to a metallizingfacility 16 where both sides of the coated and dried carrier sheet aremetallized with a thin film of vapor deposited aluminum. The resultingmulti-layer sheet is then transported for further processing to afacility at 18 where the coatings are stripped from the carrier in asolvent such as acetone to form a solvent-based slurry 20 that dissolvesthe coating from the flakes. The slurry is then subjected to sonictreatment and centrifuging to remove the acetone and dissolved coating,leaving a cake 22 of concentrated aluminum flakes. The flakes are thenlet down in a solvent and subjected to particle size control at 24 suchas by homogenizing.

[0037] This process has proved highly successful in producing extremelythin metal flakes of high aspect ratio and high specular reflectance.(Aspect ratio is the ratio of average particle size divided by averageparticle thickness.) Despite the success of the Metalure process, itwould be desirable to reduce production costs because the repeatedtransportation of the coated web between gravure coating and metallizingfacilities increases the cost of production. There is also a productioncost associated with the PET carrier not being reusable after thestripping operations.

[0038] FIGS. 2 to 5 illustrate one embodiment of a process for makingthe metal flakes shown in FIGS. 6 and 7. This process also can be usedfor making glass flakes, described below, and also can be used formaking nanospheres, as described below. FIG. 2 illustrates a vacuumdeposition chamber 30 which contains suitable coating and metallizingequipment for making the multi-layer coated flakes 32 of FIG. 7.Alternatively, certain coating equipment in the vacuum chamber of FIG. 2can be deactivated for making the single layer flakes 34 of FIG. 6, aswill become apparent from the description to follow.

[0039] Referring again to FIG. 2, the vacuum deposition chamber 30includes a vacuum source (not shown) used conventionally for evacuatingsuch deposition chambers. Preferably, the vacuum chamber also willinclude an auxiliary turbo pump (not shown) for holding the vacuum atnecessary levels within the chamber without breaking the vacuum. Thechamber also includes a chilled polished metal drum 36 on which amulti-layer sandwich 38 is produced. This embodiment of the inventionwill first be described with reference to making the flakes 32 of FIG. 7which, in one embodiment, includes an internal metallized film layer 40and outer layers 42 of a protective coating bonded to both sides of themetal film. The protective coating can comprise an inorganic material ora polymeric material, both of which are vapor deposited under vacuum.

[0040] The vacuum deposition chamber includes suitable coating and vapordeposition sources circumferentially spaced apart around the drum forapplying to the drum a solvent soluble or dissolvable release coating, aprotective outer coating, a metal layer, a further protective outercoating for the metal layer, and a further release layer, in that order.More specifically, these sources of coating and deposition equipmentcontained within the vacuum deposition chamber include (with referenceto FIG. 2) a release system source 44, a first protective coating source46, a metallizing source 48, and a second protective coating source 50.These coating and/or deposition sources are spaced circumferentiallyaround the rotating drum so that as the drum rotates, thin layers can bebuilt up to form the multi-layered coating sandwich 36 such as, forexample, in sequence:release-coating-metal-coating-release-coating-metal-coating-release, andso on. This sequence of layers built up in the multi-layer sandwich 38is illustrated schematically in FIG. 4 which also illustrates the drum36 as the carrier in that instance.

[0041] In one embodiment, the release coating is either solvent-solubleor dissolvable but is capable of being laid down as a smooth uniformbarrier layer that separates the metal or glass flake layers from eachother, provides a smooth surface for depositing the intervening metal orglass flake layers, and can be separated such as by dissolving it whenlater separating the metal or glass flake layers from each other. Therelease coating is a dissolvable thermoplastic polymeric material havinga glass transition temperature (T_(g)) or resistance to melting that issufficiently high so that the heat of condensation of the depositedmetal layer (or other flake layer) will not melt the previouslydeposited release layer. The release coating must withstand the ambientheat within the vacuum chamber in addition to the heat of condensationof the vaporized metal or glass flake layer. The release coating isapplied in layers to interleave various materials and stacks ofmaterials so as to allow them to be later separated by solubilizing therelease layer. A release layer as thin as possible is desired because itis easier to dissolve and leaves less residue in the final product.Compatibility with various printing and paint systems also is desirable.The release coating is solvent-soluble, preferably a thermoplasticpolymer, which is dissolvable in an organic solvent. Although therelease coating source 44 can comprise suitable coating equipment forapplying the polymeric material as a hot melt layer or for extruding therelease coat polymer directly onto the drum, in the preferredembodiment, the release coat equipment comprises a vapor depositionsource that vaporizes a suitable monomer or polymer and deposits it onthe drum or sandwich layer. Various examples of vapor depositionequipment for applying the polymeric release coat to the depositionsurface are described below. The release material freezes to solidifywhen it contacts either the chilled drum or the multi-layer sandwichpreviously built up on the chilled drum. The multi-layer film built upon the drum has a thickness sufficient to enable the chilled drum topull enough heat through the film so as to be effective in solidifyingthe release coat being deposited on the outer surface of the metal orglass flake layer. An alternative polymeric release coating material canbe lightly cross-linked polymeric coatings which, while not soluble,will swell in a suitable solvent and separate from the metal or glassflake material. In addition, a dissolvable release material may comprisea polymeric material which has been polymerized by chain extensionrather than by cross-linking.

[0042] Presently preferred polymeric release coatings are styrenepolymers, acrylic resins or blends thereof. Cellulosics may be suitablerelease materials, if capable of being coated or evaporated withoutdetrimentally affecting the release properties.

[0043] Presently preferred organic solvents for dissolving the polymericrelease layer include acetone, ethyl acetate and toluene.

[0044] Referring again to the process of making the flakes shown in FIG.2, and following application of the release coating, the drum travelspast the first protective coating source 46 for applying a protectivelayer to the release coat. This protective layer can be a vapordeposited functional monomer such as an acrylate or methacrylatematerial which is then cured by EB radiation or the like forcross-linking or polymerizing the coating material; or the protectivematerial can be a thin layer of radiation cured polymer which can belater broken up into flakes. Alternatively, the protective layer can bea vapor deposited inert, insoluble inorganic or glass flake materialwhich forms a hard clear coat that bonds to both sides of the metallayer. Desirable protective coatings are hard impervious materials whichcan be deposited in alternating layers with metals such as aluminum toprovide a level of wear resistance, weatherability protection, and waterand acid resistance. Examples of such protective materials are describedbelow.

[0045] The rotating drum then transports the coating past themetallizing source 48 for vapor depositing a layer of metal such asaluminum on the coating layer. A number of metals or inorganic compoundscan be deposited as a thin film interleaved by other materials andrelease layers so they can be later separated into thin metallic flakes.In addition to aluminum, such materials include copper, silver,chromium, nichrome, tin, zinc, indium, and zinc sulfide. Metal coatingsalso can include multi-directional reflection enhancing stacks (layersof highly reflective materials), or optical filters made by depositingsuitable layers of controlled thickness and index of refraction.

[0046] The rotating drum then transports the stack past the secondcoating source 50 for again applying a similar protective coating layerto the metallized film such as by vapor deposition and curing of a hardprotective polymeric material or vapor depositing an inorganic material.

[0047] Rotation of the drum then transports the sandwich material fullcircle again past the release coat source and so on in sequence to buildup the coated metal layers.

[0048] Inorganic materials such as oxides and fluorides also can bevapor deposited by the deposition source 48 so as to produce thin layersthat can be separated and made into flakes. Such coatings includemagnesium fluoride, silicon monoxide, silicon dioxide, aluminum oxide,aluminum fluoride, indium tin oxide and titanium dioxide.

[0049] Suitable deposition sources include EB, resistance, sputteringand plasma deposition techniques for vapor depositing thin coatings ofmetals, inorganics, glass flake material and polymers.

[0050] Once the multi-layer sandwich is produced in the vacuumdeposition chamber, it is then ready to be removed from the drum andsubjected to further processing illustrated in FIG. 5.

[0051] The continuous process of building up the multi-layer sandwich isdepicted at FIG. 52 in FIG. 5. The multi-layer sandwich is then strippedfrom the drum at 54 by a process in which the layers that are separatedby the releasing material are broken apart into individual layers. Thesandwich layers may be stripped by introducing them directly into anorganic solvent, or by crushing and grinding or scraping. In theillustrated embodiment, the multi-layer sandwich is subjected togrinding at 56 to produce rough flakes 58. The rough flakes are thenmixed with a suitable solvent in a slurry 60 for dissolving the releasecoat material from the surfaces of the multi-layer flakes 32.Alternatively, the multi-layer sandwich may be stripped from the drumand broken into individual layers by a step 63 of introducing thelayered material directly into the solvent at 60. The release coatmaterial applied in the vacuum deposition chamber is selected so thatthe release material is dissolvable from the flakes by the solvent inthe slurry process. In one embodiment, the slurry is subjected to acentrifuging step 61 so that the solvent or water is removed to producea cake of concentrated flakes. The cake of concentrated flakes then canbe let down in a preferred vehicle, in a particle size control step 62,to be further sized and homogenized for final use of the flakes in inks,paints or coatings, for example. Alternatively, the flakes can be letdown in a solvent (without centrifuging) and subjected to particle sizecontrol at 62.

[0052] As an alternative processing technique, the multi-layer sandwichcan be removed from the drum and “air” milled (inert gas should be usedto prevent fire or explosion) or otherwise reduced to a small particlesize, followed by treating this material in a two-step solvent process.First a small amount of solvent is used to begin the swelling process indissolving the release coat layers. A different second solvent is thenadded as a finished solvent for completing the release coat dissolvingprocess and for enhancing compatibility with the finished ink orcoating. This process avoids subsequent centrifuging and homogenizationsteps.

[0053] In an alternative embodiment for utilizing the vacuum chamber 30equipment of FIG. 2 the protective coating sources 46 and 50 can beomitted and the process can be used for making the single layer flakes34 shown in FIG. 6. In this instance the build up of layers on the drum36 to form the multi-layer sandwich 38 comprises successive layers ofrelease-metal-release-metal-release, and so on, as illustrated at 64 inFIG. 3. Alternatively, the single layer flakes can comprise layers of aninorganic or glass flake material as described above.

[0054] Many different materials and stacks of materials can beconstructed where they are sandwiched by the soluble release layers thatallow them to be separated from each other by solubilizing the releasematerial. Examples of such constructions are: (1) release/metal/release;(2) release/protective layer/metal/protective layer/release; (3)release/nonmetal layer/release; and (4) release/multi-directionalreflection enhancing stack/release.

[0055]FIGS. 8 and 9 illustrate an alternative process for making theflakes illustrated in FIGS. 6 or 7. In the embodiment illustrated inFIG. 8, the process equipment comprises a vapor deposition chamber 66which contains a chilled rotating drum 68 and a flexible insolublepolyester carrier film 70 extending from a first reversible windingstation 72 around a length of the drum's surface to a second reversiblewinding station 73. The length of wrap on the drum is controlled by twoidle rollers 74. This vacuum chamber also includes the standard vacuumpump and an auxiliary turbo pump to maintain the vacuum level duringcoating operations. Rotation of the drum causes the polyester film totravel past a first release coat source 76, a first protective coatingsource 78, a metallizing source 80, a second protective coating source82 and a second release coat source 84, in that order. Thus, as the drumrotates in a counterclockwise direction with respect to FIG. 8 theentire length of the polyester carrier is unwrapped from station 72 andtaken up on station 73 after passing through the coating processes insequence from sources 76, 78, 80, 82 and 84. The polyester carrier isthen rewound by reversing the web path and inactivating the secondrelease coating source 84 and then repeating the first step, but in areverse (clockwise) direction so that the coatings are next applied fromsources 82, 80, 78 and 76, in that order. The entire PET coated film isthen taken up on station 72 and the sequence of steps is then repeatedto build up layers on the film in the same sequence used to produce themulti-layer sandwich 38 of FIG. 4 (and the resulting coated metal flakes32 of FIG. 7).

[0056] Alternatively, in the instance in which the single layer metal orglass flakes of FIG. 6 are to be produced, the multi-layer sandwich 64illustrated in FIG. 3 is built up on the polyester carrier 70 byinactivating the protective coating sources 78 and 82.

[0057]FIG. 9 illustrates processing of the multi-layered coatingsandwich 86 built up on the polyester film which is removed from thevacuum chamber 66 and introduced into an organic solvent strippingprocess at 88 to remove the sandwich material from the PET. The solventis then subjected to centrifuging to produce a cake 90 of concentratedflakes which is later subjected to particle size control (homogenizing)at 92.

[0058] Suitable carriers on which the multi-layer sandwich material maybe deposited must ensure that the deposits of thin layers are smooth andflat. Polyester films or other polymeric films having a high tensilestrength and resistance to high temperature can be used, along withmetal drums, belts or plates which can be stainless steel or chromeplated.

[0059] In one embodiment of the invention, polymeric release coats areapplied for the purpose of facilitating later separation of the flakelayers built up in the multi-layer sandwich material. Prior art use ofcross-linked polymeric layers bonded between vapor deposited metallayers in a polymer/metal vapor deposition process inhibits laterseparation of the metallized layers into flakes. Polymerization of thepolymeric layers such as by EB curing prevents subsequent redissolvingof the polymeric layers and so the aluminum flake layers do not easilycome apart. In the present process, the intervening polymeric layers arevaporized and deposited while under vacuum in the vacuum depositionchamber. The polymeric release material is preferably a flowable lowviscosity, relatively low molecular weight very clean thermoplasticpolymer or monomer which is essentially free of any volatiles that wouldbe evolved during the coating process. Such a material is preferably nota blend of different polymeric materials including additives, solventsand the like. When the polymeric material is heated to its melt orcoating or deposition temperature, continuous operation of the vacuumpump in the vacuum chamber is not adversely affected by volatiles. Thepreferred release coat material promotes intercoat separation betweenalternating vacuum deposited metal or glass flake or multi-layer flakelayers. The release layer accomplishes this objective by beingdissolvable in a suitable organic solvent. The release material also ismetalizable and also requires sufficient adhesion to enable stackbuild-up on a rotating drum, as well as being EB vaporizable. Thedesirable release coat material must have a sufficiently high molecularweight or resistance to melting such that it resists heat build up onthe drum or other carrier without becoming flowable. Heat build up comesnot only from the metal deposited on the release layer but also fromoperation of the deposition sources inside the chamber. The ability ofthe release coat to resist flowability can ensure that flakes with highbrightness can be produced because the release coat surface on whichmetal is deposited remains smooth. The release material also must be onewhich can survive the heat of EB deposition. It must also not be amaterial, such as certain low molecular weight materials, whichdetrimentally affects vacuum pressure maintained in the chamber, say becausing the chamber to lose vacuum. Maintaining a minimum operatingvacuum level in the chamber is required to maintain production speedwithout breaking the vacuum. During subsequent stripping and treatmentwith organic solvents, essentially all of the release coat material isremoved from the flakes. However, in the event that some small amount ofrelease coat material may remain on the flakes after the flake layersare broken down into particles, the system can withstand some residuefrom the release coat, particularly if the flakes are subsequently usedin acrylic inks or paints or coating systems in which the flakes arecompatible.

[0060] Referring to the embodiment of FIG. 2, the multi-layer sandwichis made by applying the coatings directly to the rotating drum, and thisis a desirable process because it has lower production costs than theprocess of coating a PET carrier. Each such cycle involves breaking thevacuum, taking out the sandwich layer for further processing outside thevacuum chamber and re-charging the vacuum. The rate at which the processcan be run, in building up layers, can vary from approximately 500 to2,000 feet per minute. Metallizing only in the vacuum can operate athigher speeds.

[0061] In the embodiments in which the single layer flakes are produced,the flakes can have high aspect ratios. This is attributed, in part, tothe capability of cleanly removing the intervening release coat layersfrom the metallized flakes. With thermoset or cross-linked polymericlayers bonded in between the metal layers, the layers cannot be easilyseparated and resulting flakes have lower aspect ratios. In oneembodiment, the process of this invention produces single layerreflective aluminum flakes approximately 5 to 500 angstroms thick, andapproximately 4 to 12 microns in particle size.

[0062] The release coat materials are applied in exceedingly thin layerspreferably about 0.1 to about 0.2 microns for coated layers and about100 to 400 angstroms for EB deposited layers.

[0063] In the embodiments in which the metal flakes are coated onopposite sides with the protective polymeric film layers, the protectivecoating layers are applied at a thickness of about 150 angstroms orless. A preferred protective coating material is silicon dioxide orsilicon monoxide and possibly aluminum oxide. Other protective coatingscan include aluminum fluoride, magnesium fluoride, indium tin oxide,indium oxide, calcium fluoride, titanium oxide and sodium aluminumfluoride. A preferred protective coating is one which is compatible withthe ink or coating system in which the flakes are ultimately used. Useof the protective coatings on the metal flakes will reduce aspect ratioof the finished flake product, although the aspect ratio of thismulti-layer flake is still higher than the ratio for conventionalflakes. However, such flakes are more rigid than the single layerflakes, and this rigidity provided by the clear glass-like coated metalflakes can, in some instances, make the coated flakes useful influidized bed chemical vapor deposition (CVD) processes for applyingcertain optical or functional coatings directly to the flakes. OVDcoatings are an example. CVD coatings can be added to the flakes forpreventing the flakes from being prone to attack by other chemicals orwater. Colored flakes also can be produced, such as flakes coated withgold or iron oxide. Other uses for the coated flakes are inmoisture-resistant flakes in which the metal flakes are encapsulated inan outer protective coat, and in micro-wave active applications in whichan encapsulating outer coat inhibits arcing from the metal flakes. Theflakes also can be used in electrostatic coatings.

[0064] In an alternative embodiment there may be instances in which therelease coat layers comprise certain cross-linked resinous materialssuch as an acrylic monomer cross-linked to a solid by UV or EB curing.In this instance the multi-layer sandwich is removed from the drum, orwhile on the carrier, it is treated with certain materials thatde-polymerize the release coat layers such as by breaking the chemicalbonds formed from the cross-linking material. This process allows use ofconventional equipment utilizing vapor deposition and curing with EB orplasma techniques.

[0065] The process of this invention enables production of reflectiveflakes at high production speeds and low cost. The uncoated flakesproduced by this invention can have a high aspect ratio. Where aspectratio is defined as the ratio of particle size to thickness, and theaverage flake size is approximately 6 microns by 200 Angstroms (onemicron=10,000 Angstroms) the aspect ratio 60,000/200 is or about 300:1.This high aspect ratio is comparable to the Metalure flakes describedpreviously. For the embodiments in which flakes are coated on both sideswith protective layers, the aspect ratio of these flakes isapproximately, 60,000/600 or about 100:1.

[0066] Embossed flake also can be made by the process of this invention.In this instance, the carrier or deposition surface (drum or polyestercarrier) can be embossed with a holographic or diffraction gratingpattern, or the like. The first release layer will replicate thepattern, and subsequent metal or other layers and intervening releaselayers will replicate the same pattern. The stack can be stripped andbroken into embossed flakes.

[0067] One process for speeding production of the flake products made bythis invention utilizes three side-by-side vacuum chambers separated byair locks. The middle chamber contains a drum and the necessarydeposition equipment for applying the layers of flake material andrelease coats to the drum. When the deposition cycle is completed, thedrum and coating are transferred to the vacuum chamber downstream fromthe deposition chamber, through the air lock, for maintaining the vacuumin both chambers. The middle chamber is then sealed off. A drumcontained in the upstream chamber is then moved to the middle chamberfor further deposition. This drum is moved through an air lock tomaintain the vacuum in both chambers. The middle chamber is then sealedoff. The coated drum in the downstream chamber is removed, stripped ofits deposited layers, cleaned and replaced in the upstream chamber. Thisprocess enables continuous coating in the middle vacuum chamber withoutbreaking its vacuum.

EXAMPLE 1

[0068] The following multi-layer construction was made: releaselayer/metal/release layer. The release layer was Dow 685D extrusiongrade styrene resin and the metal layer was aluminum from MaterialsResearch Corp. 90101E-AL000-3002.

[0069] The construction was repeated 50 times, i.e., alternating layersof aluminum and styrene release coats.

[0070] The styrene used in the release layer was conditioned as follows:

[0071] The styrene pellets were melted and conditioned in a vacuum ovenat 210° C. for 16 hours and then removed to a desiccator to cool.

[0072] An aluminum foil lined graphite crucible was used to hold thismaterial.

[0073] This crucible was placed in a copper lined Arco Temiscal singlepocket electron beam gun hearth.

[0074] The aluminum pellets were melted into a copper lined ArcoTemiscal four-pocket electron beam gun hearth.

[0075] The electron beam guns were part of a 15 KV Arco Temiscal 3200load-lock system. Two mil PET film from SKC was cut into three seventeeninch diameter circles and attached to seventeen inch diameter stainlesssteel planetary discs located in the vacuum chamber. The chamber wasclosed and roughed to ten microns then cryopumped to a vacuum of 5×10−7Torr.

[0076] The release and metal material were vapor deposited inalternating layers. The release layer was deposited first at 200angstroms as measured by a Inficon IC/5 deposition controller. Therelease layer was followed by a metal layer vapor deposited at 160angstroms also measured by the IC/5 controller. The controller for thealuminum layer was calibrated by a MacBeth TR927 transmissiondensitometer with green filter. As mentioned, this construction wasrepeated 50 times. The vapor deposited aluminum layer had a goodthickness of 1.8 to 2.8 optical density as measured by a MacBethdensitometer. This value measures metal film opacity, via a lighttransmission reading.

[0077] When the deposition was complete, the chamber was vented withnitrogen to ambient pressure and the PET discs removed. The discs werewashed with ethyl acetate then homogenized using a IKA Ultra Turrax T45to reach a particle size of 3 by 2 microns, measured on Image-pro plusimage analyzer using a 20× objective and averaged from a set of 400particles.

[0078] The dispersion was then made into an ink and drawn down on aLenetta card for ACS spectrophotometer testing. This test measures flakebrightness. An ACS value above about 68 is considered desirable for thisparticular product. ACS readings were 69.98 for the Metalure control and70.56 for the batch. The inks were drawn down on clear polyester anddensity readings were 0.94 for the batch and 0.65 for the Metalurecontrol. Readings were taken on a MacBeth densitometer using a greenfilter.

EXAMPLE 2

[0079] The following multi-layer construction was made: releaselayer/protective coat/metal/protective coat/release layer.

[0080] Three separate constructions were made as follows: Construction 1REL Dow 685D PROT Cerac Silicon Oxide S-1065 MET Materials ResearchCorp. 90101E-AL000-3002 PROT Cerac Silicon Oxide S-1065 REL Dow 685DConstruction 2 REL Dow 685D PROT Cerac Aluminum Oxide A-1230 METMaterials Research Corp. 90101E-AL000-3002 PROT Cerac Aluminum OxideA-1230 REL Dow 685D Construction 3 REL Dow 685D PROT Cerac MagnesiumFluoride M-2010 MET Materials Research Corp. 90101E-AL000-3002 PROTCerac Magnesium Fluoride M-2010 REL Dow 685D

[0081] The construction were repeated ten times by the same processdescribe in Example 1 and were evaluated as protective coated flake,i.e., this test indicated that multi-layer flakes having optical utilitycould be made by building up the layers of flake material on a carrierin a vacuum chamber between intervening layers of dissolvable releasematerial, in which the flake layers are built up continuously (withoutbreaking the vacuum) while depositing the release layers and flakelayers from deposition sources operated within the vacuum chamber,followed by stripping, and particle size control.

EXAMPLE 3

[0082] The following multi-layer constructions were made: Construction 1REL Dow 685D NONMET Silicon Oxide S-1065 REL Dow 685D Construction 2 RELDow 685D Stack Titanium Dioxide Cerac T-2051 Stack Silicon Oxide CeracS-1065 + Oxygen MET Materials Research Corp. 90101E-AL000-3002 StackSilicon Oxide Cerac S-1065 + Oxygen Stack Titanium Dioxide Cerac T-2051REL Dow 685D

[0083] The construction was repeated ten time by the same processdescribed in Example 1. This test indicated that the process of vapordeposition can form built-up layers of optical stacks betweenintervening release coat layers in a vacuum chamber, followed bystripping and particle size control, which yielded flakes having utilityfor such applications as inks and coatings.

EXAMPLE 4

[0084] The following constructions may be possible constructions fordecorative flake: Construction 1 REL Dow 685D Stack Iron Oxide CeracI-1074 Stack Silicon Oxide Cerac S-1065 + Oxygen Stack Iron Oxide CeracI-1074 REL Dow 685D Construction 2 REL Dow 685D Stack Iron Oxide CeracI-1074 Stack Silicon Oxide Cerac S-1065 + Oxygen MET Aluminum MaterialsResearch Corp. 90101E-AL000- 3002 Stack Silicon Oxide Cerac S-1065 +Oxygen Stack Iron Oxide Cerac I-1074 REL Dow 685D

[0085] The constructions also maybe used for a gonio chromatic shift.

EXAMPLE 5

[0086] Polymeric release coat layers were deposited in a vacuum chamber,using an EB source, and coated with a vapor deposited aluminum layer.

[0087] The following constructions were made:

[0088] Construction 1

[0089] Dow 685D styrene resin was conditioned in an oven for 16 hours at210° C. The material was EB deposited on polyester at a thickness of 200to 400 angstroms and metallized with one layer of aluminum at densitiesof 2.1 to 2.8.

[0090] Construction 2

[0091] Piolite AC styrene/acrylate from Goodyear was conditioned for 16hours at 190° C. The material was EB deposited on polyester at a coatweight of 305 angstroms metallized with one layer of aluminum at adensity of 2.6.

[0092] Construction 3

[0093] BR-80 acrylic copolymer from Dianol America was conditioned for16 hours at 130° C. The material was EB deposited on polyester at athickness of 305 angstroms metallized with one layer of aluminum at adensity of 2.6.

[0094] Construction 4

[0095] Dow 685D styrene resin was conditioned for 16 hours at 210° C.The material was EB deposited on polyester at a thickness of 200angstroms and metallized with one layer of aluminum at a density of 2.3.This was repeated to form a stack of 10 layers of aluminum separated bythe intervening release coat layers.

[0096] These layered materials were stripped from the PET carriers usingethyl acetate solvent and reduced to a controlled particle size in a T8lab homogenizer. The resulting flakes were similar in optical propertiesto Metalure flakes, in that they had similar brightness, particle size,opacity and aspect ratio.

[0097] In a further test with a construction similar to Construction 1,aluminum metalized to an optical density of 2.3 was stripped from a PETcarrier in acetone and broken into flakes. This test observed the effectof release coat thickness changes. The results indicated best releaseproperties with an EB deposited release coat in the range of about 200to about 400 angstroms.

EXAMPLE 6

[0098] Several tests were conducted to determine various polymericrelease coat materials that may be useful in this invention. LaboratoryBell Jar tests were conducted to determine polymers that maybe EBdeposited. Methyl methacrylate (ICI's Elvacite 2010) and a UV-curedmonomer (39053-23-4 from Allied Signal) produced good results. Poorresults were observed with butyl methacrylate (Elvacite 2044) (losesvacuum in EB), cellulose (turned black at 280° F), and polystyrenerubber (charred).

EXAMPLE 7

[0099] The tests described in Example 1 showed that a release coat madefrom the Dow 685D styrene polymer could produce usable flake products.Several other tests were conducted with Dow 685D styrene resin releasecoats as follows:

[0100] (1) Conditioned at 190° C., coated at 1,000 angstroms andmetalized with aluminum. Resin film built too high produced a hazymetalized layer.

[0101] (2) Not conditioned in oven; when attempting to EB melt thestyrene beads the E-Beam caused the beads to move in the crucible.

[0102] (3) Conditioned at 210° C., coated from 75 to 150 angstroms thenmetalized. Aluminum stripped poorly or not at all.

[0103] (4) Conditioned at 210° C., coated at 600 angstroms and metalizedone layer of aluminum at 1.9 density. Aluminum stripped slowly andproduced a curled flake.

[0104] This invention makes it possible to produce thin decorative andfunctional platelets of single or multilayer materials with thicknessfrom about 5 to about 500 angstroms single layer, from about 10 to 2000angstroms multilayer, with average outer dimensions from about 0.01 to150 micrometers. The flakes or particles made by the process of thisinvention are referred to as angstrom scale particles because they areuseful flake material that can be made with a thickness in the lowangstrom range mentioned above. Some particles made by this inventioncan be characterized as nanoscale particles. As is well known, 10angstroms equals one nanometer (nm), and the nanoscale range isgenerally from one to 100 nm. Thus, some of the angstrom scale particles(thickness and/or particle size) of this invention fall within thenanoscale range.

[0105] These particles can be used as functional platforms by themselvesor coated with other active materials. They can be incorporated into orcoated onto other materials. As mentioned above, they are produced bydepositing materials or layers of materials such that the mono ormultilayered platelets are interleaved with polymeric releasing layers.The supporting system for these layer sandwiches can be a plate, film,belt, or drum. The functional materials can be applied by PVD (physicalvapor deposition) processes and the releasing layers can be applied byPVD.

[0106] Once the sandwich layers with the interleaving releasing layersare formed the material can be removed from the supporting system andfunctional layers can be separated from the releasing layers. This canbe done cryogenically, with the appropriate solvent, or with asupercritical fluid. The resulting material can be turned into plateletsand sized by grinding, homogenizing, sonolating, or high-pressureimpingement.

[0107] Centrifuging or filtering results in a cake, slurry, or driedmaterial. Other active materials can be added to the particles via CVDor reacted with materials such as silanes to promote adhesion. Then thematerials can then be incorporated into or coated onto the desiredmaterial such as paints, coatings, inks, polymers, solids, solutions,films, fabrics, or gels, for functional uses.

[0108] Various angstrom scale flake constructions of this inventioninclude (1) aluminum, metal alloy and other metal (described below)monolayer flakes; (2) single layer dielectrics, inorganic orcross0linked polymer flakes; (3) multi-layer inorganics; (4) opticalstacks; (5) inorganic or organic/metal/inorganic or organic multilayerflakes; (6) metal/inorganic/metal flakes/ and (7) CVD or chemicallyreacted surface coated flakes.

[0109] The uses for these nanoscale and high aspect ratio particles areas follows.

[0110] Optical Aesthetic

[0111] High aspect ratio materials can provide bright metallic effectsas well as colored effects. Metals such as aluminum, silver, gold,indium, copper, chromium or alloys and metal combinations such asaluminum copper, copper zinc silver, chromium nickel silver, titaniumnitride, titanium zirconium nitride and zirconium nitride may be used toproduce these materials. Sandwiches of metals and dielectric materialscan produce various colors and effects. Inert materials can be used asthe outside layer to protect the inner layers from oxidation andcorrosion. Examples of some sandwiches are SiO/Al/SiO, MgF/Al/MgF,Al/SiO/Al, Al/MgF/Al, but many other combinations are possible. Flakesof metal or metal oxides can be used as a base to attach both organicand inorganic materials that provide pigment-like colors.

[0112] Optical Functional

[0113] Nanoscale and high aspect ratio particles can have manyapplications that take advantage of optical properties. Particles ofaluminum oxide, titanium dioxide, zinc oxide, indium tin oxide, indiumoxide can be incorporated into coatings and polymers to reflect,scatter, or absorb UV and IR light. Also phosphorescent and fluorescentmaterials can be used to produce other important effects.

[0114] Mechanical

[0115] These particles can be incorporated into or applied to thesurface of materials to enhance their properties. Particles of siliconmonoxide, aluminum dioxide, titanium dioxide, and other dielectrics canbe incorporated into materials to improve properties such as flameretardancy, dimensional stability, wear and abrasion resistance,moisture vapor transmission, chemical resistance, and stiffness.

[0116] Chemical

[0117] Active materials can be applied to the surface of these particlesto provide small high surface areas that can be introduced into chemicalprocesses. These high surface area particles are ideal for catalysts.They can be platelets of the active material or flakes made to supportan active coating. Examples of active materials are platinum, palladium,zinc oxide, titanium dioxide, and silicon monoxide. Flakes produced frommetal (lithium) doped materials may have uses in batteries.

[0118] Electrical

[0119] Electrical properties can be imparted to various materials andcoatings by incorporating particles of various materials as bothmonolayers and multilayers to effect conductivity, capacitance, EMI, andRFI. The absorption, transmission, and reflectance of microwave andradar energy can be modified by coating or incorporating particles ofmetals or metal dielectric sandwiches. Superconducting materials such asmagnesium boride also can be made into angstrom scale particles.

[0120] Biological

[0121] By placing an anti fungal or antibacterial coating on these thinplatelets then incorporating them into inks and coating active agentscan be effectively transported to the surfaces .

[0122] Nanoparticles

[0123] Nanoparticles can be produced by vapor depositing a flakematerial as discrete particles. In the industry it is well known thatnucleation and film growth play an important role in formation ofquality PVD coatings. During the initial deposition nuclei are formedthat grow in size and number as the deposition continues. As the processcontinues these islands begin to join together in channels that laterfill in to form the final continuous film. To make nanoparticles, thecoating process only reaches the island stage before the next layer ofreleasing material is applied. This allows the small particles to betrapped between the releasing layers in the multilayer constructiondescribed below. They can later be released by dissolving the releasingmaterial with the proper solvent.

[0124] Another process for making nanoscale particles is to produce theflake material below 50 angstroms and then reduce the particle diameterwith a secondary operation.

[0125] Use of Flake Material in Coatings

[0126] Flake material was put into a coating for use in the aboveapplications using the following procedure:

[0127] Various material compositions of materials were converted intoflake form. The converted flake was then incorporated, on a surface areabasis, into a vehicle. Vehicle Composition: Toluene 28 pts Isopropanol28 pts Methyl Ethyl Ketone 28 pts Elvacite 2042 16 pts

[0128] The actual weight of the flake used in this example was derivedby the thickness and the density of the chemical compound. Thisderivation was used to study the effect of the chemical compound. Theflake was supplied in a slurry form in acetone. The first step in theprocess was to measure the percent solids by weight. After finding thesolids, the amount of slurry material to use can be determined by thefollowing table. Dry flake per Weight to use Thickness of 100 g vehiclePercent wt per 100 g Material Density the Flake solution solids ofslurry vehicle sol. Titanium 4.26 200 A 0.09 g Dioxide Titanium 4.93 200A 0.08 g Monoxide Silicon Dioxide 2.2 200 A 0.20 g Silicon 2.13 200 A0.20 g Monoxide Aluminum 3.97 200 A 0.10 g Oxide Indium Oxide 7.13 200 A0.06 g Indium Tin 4.48 200 A 0.09 g Oxide Zinc Oxide 5.6  75 A 0.03 gIndium 7.3 200 A 0.06 g Magnesium 3.18 200 A 0.13 g Fluoride Silicone2.33 200 A 0.16 g

[0129] The flake was mixed into the vehicle at the appropriate weight.The slurry was then coated onto a gloss polyester film, 0.002 inchesthick, to achieve a final coating thickness of 2.6 to 3.0 g/m². Thecoating was allowed to dry then tested in two ways.

[0130] Method for Evaluating Heat Reflective Properties

[0131] The prepared coatings were transferred to the surface of a sheetof rigid polyvinyl chloride (PVC) decorated with EF18936L using heat andpressure. The polyester film was removed after transfer. Three inch bythree inch panels were prepared with a blank (vehicle without flake) andthe test flake. These panels were then evaluated using the ASTM D4809-89method for predicting heat buildup in PVC building products. The resultswere reported for both the blank and the test flake panel.

[0132] Method of Evaluating UV Screening Properties

[0133] A base test sheet was prepared by applying a film comprising ofthe following materials to a rigid PVC sheet: Color Coat I80126 Vehicle59.5 pts I80161 White Dispersion 27.0 pts I8980 Isoindolinone Yel Disp5.4 pts MEK Methyl Ethyl Ketone 8.1 pts

[0134] Apply to 0.002 mil gloss polyester using 2-137HK printing plates

[0135] Size L56537

[0136] Apply after color coats using 1-137HK printing plate

[0137] The blank and slurry are prepared on polyester as in the previousmethod and transferred to the panels described above. Both the blank andthe test flake panel are placed in a Sunshine Carbon Arc (Atlas)weatherometer set up on the Dew Cycle protocol. Initial gloss and colorreadings are taken and recorded every 500 hours of operating time.

[0138] The multilayer particle releasing layer can be made fromconventional organic solvent-based polymers deposited in a PVD process.A number of different materials can be used such as polymers, oligimers,and monomers. These materials can be evaporated by electron beam,sputtering, induction, and resistance heating.

[0139] One of the difficulties with using bulk polymer in this processis to effectively feed the polymer into the evaporating system withoutits being exposed for long periods of time to high temperature, whichcan have detrimental effects. Another difficulty is evaporating andconducting the polymer vapor to the support system while notcontaminating the vacuum system or degrading the vacuum.

[0140] Several approaches can overcome these problems with polymerdelivery. One approach is to coat the polymer onto a carrier materialsuch as a wire or ribbon made of metal or material that can withstandthe temperatures of vaporization. This coated material is then fed intothe polymer vapor die where it is heated and the polymer is vaporizedand the vapor is conducted to the support system. Another approach is tomelt the polymer and reduce its viscosity and then extrude or pump thematerial into the polymer vapor die. A gear pump, extruder, or capillaryextrusion system (Capillary Rehometer) like the polymer vapor die canprovide a vaporizing surface that is heated to the appropriatetemperature. The die then conducts the vapor to the support system. Itis necessary to provide a cooled surface to condense any stray polymervapor that leaves the polymer die support system area and differentiallypump this area as well.

[0141] Bell Jar Process

[0142] Referring to FIG. 10, a vacuumizable bell jar 100 is modifiedwith a heater block 102 installed on the floor of the bell jar. Theblock comprises a heated polymer vapor chamber 104 having a cavity 106carved out to hold the desired sample. A crucible 108 made of aluminumfoil is fitted to the block and approximately 0.3 g of the desiredmaterial is placed in the crucible. The crucible is then placed in theheater block.

[0143] Above the heater block, a deposition gauge 109 is positioned oneinch from the top of the block. As the block is heated, this gauge willmeasure the amount of material evaporated in angstroms per second(Å/sec).

[0144] Above the deposition gauge, a polyester sheet 110 is clampedbetween two posts (not shown). The material evaporated from the block isdeposited on this film. In another step, this film is metallized.

[0145] Once the sample, deposition gauge, and polyester film are inplace, the bell jar is closed and the vacuum cycle is started. Thesystem is evacuated to a pressure between 2×10⁻⁵ torr and 6×10⁻⁵ torrand the trial is ready to begin.

[0146] The heater block begins at approximately room temperature. Oncethe desired vacuum is achieved, power to the block is turned on. Theblock is set to ramp up to 650° C. in a 20 minute interval. Measurementsare taken every minute. The time, current block temperature (° C.),deposition gauge reading (Å/sec), and current vacuum pressure (torr) aredocumented each minute. The trial ends when either the deposition gaugecrystal fails or when all of the material has been evaporated and thedeposition gauge reading falls to zero.

[0147] At the end of the trial, the bell jar is opened to atmosphere.The polyester is removed and set aside to be metallized and the spentcrucible is discarded. The data is then charted for comparison to allother materials run.

[0148] Bell Jar Polymer Trials

[0149] Several experiments were run on different polymers in the belljar metallizer. The procedure described in “Bell Jar Procedure” wasfollowed for all of these experiments. For each experiment, the trialtime, temperature, deposition gauge reading, and vacuum pressure weredocumented. From these data it can be determined what materials havegreater effect on the vacuum and which material provide the highestdeposition rates. A higher deposition rate means an eventualmanufacturing sized apparatus will be able to run at higher speeds.However, materials that have greater effects on the vacuum pressurecould cause cleanup and possible pump down problems after extendedperiods of operation.

[0150] Trials 1, 2, 6, and 7 were run using the Dow 685D polystyrene.This polymer has a reported molecular weight of about 300,000. All fourtrials produced similar results. Deposition rates held at around 10Å/sec until a temperature of approximately 550° C. was reached. Up untilthat temperature, there was very little effect on the vacuum. Thepressure was generally raised less than 2×10⁻⁵ torr. Above 550° C. therate rose dramatically and the pressure rose into the range of 1.2×10⁻⁴to 1.8×10⁻⁴ torr. This is still a minimal impact on the vacuum pressure.

[0151] Trial 3 was run with Elvacite 2045, an isobutyl methacrylate witha molecular weight of 193,000. The deposition rose as high as 26.5 Å/secat a temperature of 500° C. At this temperature the vacuum pressure hadrisen to 3.6×10⁻⁴ torr from a starting pressure of 5.2×10⁻⁵ torr.

[0152] The fourth trial used Elvacite 2044, which is an n-butylmethacrylate material with a molecular weight of 142,000. Deposition forthe 2044 reached a peak of 30 Å/sec at 500° C. At this temperature thevapor pressure reached 2.0×10⁻⁴ torr.

[0153] Trials 5 and 19 were run with Endex 160, which is a copolymermaterial. The Endex 160 reached its maximum deposition at 413° C. with arate of 11 Å/sec. The deposition had almost no impact on the vacuum asit was ultimately only raised by 1.0×10⁻⁶ torr to a final reading of4.4×10⁻⁵ torr.

[0154] The eighth trial was run with Elvacite 2008, a methylmethacrylate material with a molecular weight of 37,000. The highestdeposition rate was achieved at 630° C. with a rate of 67 Å/sec. Thefinal vacuum pressure was raised to 1.0×10⁻⁴ torr.

[0155] Trials 9 and 10 were run with Piccolastic D125. This material isa styrene polymer with a molecular weight of 50,400. Deposition rates of108 Å/sec were reached at 500° C. and throughout the trials there wasminimal impact on the vacuum.

[0156] Trials 11 and 12 were run with Piccolastic A75. This is anotherstyrene monomer, but with a low molecular weight of 1,350. Depositionrates started very early and rose to a maximum of 760 Å/sec when thetemperature reached 420° C. For both trials there was once again veryminimal impact on the vacuum pressure.

[0157] Trials 13 and 14 were run with a 50,000 MW polystyrene standardfrom Polyscience. These samples have very tight molecular weightdistributions. For these trials, a deposition of 205 Å/sec was achievedat a temperature of 560° C. At that deposition, the vacuum pressure roseto 6.2×10⁻⁵ torr, a rise of 1.4×10⁻⁵ torr over the starting pressure.

[0158] Trials 15 and 16 were run with another polystyrene standard fromPolyscience, but this one had a molecular weight of 75,000. Depositionreached a rate of about 30 Å/sec at a temperature of 590° C. At thistemperature, the vacuum pressure had risen to 3.0×10⁻⁴ torr, a fairlysignificant rise.

[0159] Trial 17 was run with Endex 155, a copolymer of aromatic monomerswith a molecular weight of 8,600. The maximum deposition was reached at530° C. with a rate of 78 Å/sec. At the end of the trial the vacuumpressure had risen to 1.0×10⁻⁴ torr.

[0160] Trial 18 was another polystyrene standard from Polyscience. Thissample had a molecular weight range of 800-5,000. Deposition was as highas 480 Å/sec at a temperature of 490° C. There was little to no impacton the vacuum pressure during the entire run.

[0161] Trial 20 was run with a standard of polymethyl methacrylate fromPolyscience. This sample had a molecular weight of 25,000. A finaldeposition rate was achieved at 645° C. with a rate of 50 Å/sec. At thiscondition, the vacuum pressure had risen to 1.0×10⁻⁴ torr.

[0162] Trial 21 was run with Elvacite 2009, a methyl methacrylatepolymer treated to contain no sulfur. The molecular weight of thismaterial was 83,000. A final deposition rate of 26 Å/sec was reached ata temperature of 580° C. The vacuum pressure had risen to 1.8×10⁻⁴ torrfrom an initial reading of 4.2×10⁻⁵ torr.

[0163] Trials 22 and 26 were run with Elvacite 2697, a treated versionof a methyl/n-butyl methacrylate copolymer. The molecular weight of thismaterial was 60,000. The Elvacite 2697 had a final deposition rate of 20Å/sec at a temperature of 580° C. Vacuum pressure rose to 1.0×10⁻⁴ torrat the end of the trial.

[0164] Trial 23 was run with Elvacite 2021C, a treated methylmethacrylate. This material had a molecular weight of 119,000. A finaldeposition rate of 30 Å/sec was reached at 590° C. This trial had asignificant impact on the vacuum as the final pressure was 4.4×10⁻⁴torr, an order of magnitude increase over the initial vacuum pressure.

[0165] Trial 24 was run with Lawter K1717, apolyketone. A maximumdeposition rate of 300 Å/sec was reached at 300° C. At this temperaturethe vacuum pressure had risen to 7.0×10⁻⁵ torr. At the end of the trial,a great deal of soot remained in the crucible. This indicated that someof the material had actually combusted rather than just beingevaporated.

[0166] Trial 25 was run with Solsperse 24000, a dispersing agent. Thissample also left a soot residue in the crucible indicating combustionduring the trial. However, there was a deposition rate recorded up to100 Å/sec at 360° C. The vacuum pressure rose 1.0×10⁻⁵ torr over thecourse of the experiment.

[0167] Trial 27 was run with Elvacite 2016, a non-treated methyl/n-butylmethacrylate copolymer. This has a molecular weight of 61,000. At 630°C., the deposition rate reached 135 Å/sec. At this condition, the vacuumpressure had been significantly raised to 3.0×10⁻⁴ torr.

[0168] Trial 28 was run with Elvacite 2043, an ethyl methacrylatepolymer with a molecular weight of 50,000. At 600° C., the depositionrate was at 98 Å/sec. At this condition, the vacuum pressure was at1.0×10⁻⁴ torr.

[0169] Trial 29 was run with Kraton G1780. This material is a multiarmcopolymer of 7% styrene and ethylene/propylene. Deposition reached ahigh of 70 Å/sec at a temperature of 600° C. The final vacuum pressurerose to 8.2×10⁻⁵ torr. During the trial, the deposition rate held verysteady and did not exhibit wild fluctuation that is common in all of theother trials, especially at higher temperatures.

[0170] Trial 30 was run with Kraton G1701. This material is a lineardiblock polymer of 37% styrene and ethylene/propylene. An ultimatedeposition rate of 102 Å/sec was reached at a temperature of 595° C. Thevacuum pressure was at 8.6×10⁻⁵ torr at this final condition.

[0171] Trial 31 was run with Kraton G1702. This is a linear diblockpolymer of 28% styrene and ethylene/propylene. A final deposition rateof 91 Å/sec was reached at 580° C. The vacuum pressure had risen to8.0×10⁻⁵ torr at this condition.

[0172] Trial 32 was run with Kraton G1730M. This is a linear diblockpolymer of 22% styrene and ethylene/propylene. The maximum depositionrate of 80 Å/sec was reached at 613° C. At this temperature, the vacuumpressure was 8.0×10⁻⁵ torr.

[0173] Trial 33 was run with 1201 Creanova, a synthetic resin based on aurethane modified ketone aldehyde. This material achieved a depositionrate of 382 Å/sec at a temperature of 535° C. At this temperature therewas minimal impact on the vacuum.

[0174] Trial 34 was run with Kraton G1750M. This is a multiarm copolymerof 8% styrene and ethylene/propylene. A deposition rate of 170 Å/sec wasreached at 625° C. At this condition, the vacuum pressure rose to 9×10⁻⁵torr.

[0175] From these trials we reached the following conclusions. Thegreatest value of these experiments came from quantifying the effectvarious resins have on vacuum pressure. From the trials there appearedto be a correlation with molecular weight to the vacuum impact. Thelower the molecular weight of the material, the less impact theevaporated material will have on the vacuum pressure of the system.There does not appear to be a correlation between temperature anddeposition.

[0176] Drum with Block Procedure

[0177] Referring to FIGS. 11 and 12, a vacuumizable chamber 112 containsa rotating drum 114, a deposition gauge 116, and a heater block 118. Theheater block comprises a heated polymer vapor chamber 120 fitted with acrucible 122 having a polymer source 124. The drum 114 is approximatelyone foot in diameter and six inches wide on the surface. It can rotateat a maximum speed of two rotations per minute. The heater block iscylindrical in shape with a slot 126 carved into one area. The slot isopen into a cavity 128 running through the center of the block. Theblock has three independent heaters that can be used to control thetemperature of the block. The deposition gauge 116 is placedapproximately one inch in front of the slot. It can measure the amountof material passing through the slot in angstroms per second (Å/sec).This embodiment depicts an electron beam gun 130 in the vacuum chamber,but for this procedure, the EB gun is not used. This procedure can beused to screen polymers to determine their capability of being vapordeposited and therefore usable as a polymeric release coat.

[0178] To prepare a sample, the heater block can be opened and materialis loaded into the cavity. Once this is done, the chamber is closed andthe vacuum cycle is started. The chamber is evacuated until the pressuregets to at least 6×10⁻⁵ torr.

[0179] The block begins at around room temperature. Once the desiredvacuum is achieved, power to the three heaters is turned on. The heatersare set to ramp up to the desired temperature in a 20-minute interval.Measurements are transmitted to a computer file approximately every sixseconds. The time, block temperature in three zones (° C.), depositiongauge reading (Å/sec), and current vacuum pressure (torr) aredocumented. The trial ends when either the deposition gauge crystalfails or when all of the material has been evaporated and the depositiongauge reading falls to zero.

[0180] At the end of the trial, the chamber is opened to atmosphere. Thedeposition crystal is changed and the block is loaded with new materialfor the next trial.

[0181] Polystyrene Trials in Polymer Block

[0182] Six separate trials were run using the Dow 685D polystyrene ineach trial. This polystyrene is reported to have a molecular weight ofapproximately 300,000. In the trials, the ultimate block temperature wasvaried as well as the ramp time to reach the final temperature.

[0183] In trial 1, the block was programmed to reach 300° C. in a ramptime of 10 minutes. As the trial progressed, the polymer deposition ratewas very low at no higher than 5 Å/sec. This rate held during the entiretrial.

[0184] In the second trial the block was programmed to reach a finaltemperature of 325° C. with no ramp time set. The controllers wereallowed to increase the temperature at their maximum possible rate. Astemperature was reached, the deposition rate leveled out at about 30Å/sec. With some fluctuation, this rate held constant until 15 minutesinto the trial when the rate began to noticeably drop. By the end of thetrial at 20 minutes, the rate had fallen to 15 Å/sec. This rate decreaseis likely due to the exhaustion of the polymer supply.

[0185] In the third trial the block was set to reach an ultimatetemperature of 350° C. in a ramp time of 10 minutes. As the temperaturewas reached, the deposition rate was at about 6 Å/sec. As the trialprogressed the rate finally reached a peak of 14 Å/sec about 13 minutesinto the experiment. By the end of the trial at 20 minutes the rate hadfallen back to about 6 Å/sec. Polystyrene is theorized to begin adepolymerization at about 350° C. The deposition rate in the experimentmay have been lower because the temperature was causing thisdepolymerization as well as the evaporation that would be sensed up bythe deposition gauge.

[0186] Trial 4 had a 375° C. setpoint with no ramp to temperature. Thedeposition rate rose to 30-35 Å/sec in about 10 minutes, but did nothold steady there. As the temperature passed 350° C., the rate rosesignificantly and became erratic. The rate fluctuated from 40-120 Å/secwith no regular pattern. After 15 minutes of trial time, the depositiongauge crystal failed and the experiment was stopped. Above 350° C. thepolymer has absorbed enough energy to depolymerize, so from that pointon it liberates very low molecular weight material at high rates. Thismaterial includes monomers and dimers of the original polystyrene. Thislow end material is not useful in forming a polymer film.

[0187] The fifth trial also had a 375° C. final temperature, but thistime with a 10 minute ramp time. The deposition was very steady atfirst, but once again above 350° C. the deposition became erratic. Therate fluctuated from 20 Å/sec to a peak of 110 Å/sec. The trial ended atabout 18 minutes when the gauge crystal failed.

[0188] The final trial was at a 375° C. temperature, but with a 20minute ramp time. The same behavior was exhibited as the previous twotrials. Up to a temperature of 350° C. the deposition was fairly steadyat a rate of about 20 Å/sec. As the temperature rose through 350° C.though, the rate once again became erratic. The rate fluctuated between30 and 140 Å/sec and crystal failure once again caused the end of theexperiment, this time at 23 minutes.

[0189] From these trials we reached the following conclusions. Itappears that polystyrene exhibiting depolymerization or other physicalbreakdown at a temperature of approximately 350° C. is shown to be truein these experiments. In the trials above that temperature, the erraticbehavior occurred at approximately the same temperature in all threecases. In the trial at 350° C., the deposition rate indicated anotherprocess was taking place since a higher rate was seen at the lower 325°C. setpoint. Unless a depolymerization or other process was takingplace, the deposition rate at 350° C. should have been higher than therate at 325° C. Also, for the trials at 375° C., an oily film wasobserved at the end of the trial. This material was shown to bepolystyrene under FTIR analysis and the oily nature indicates it islikely a low molecular weight species of the polystyrene. This isfurther evidence that the original polymer (300,000 MW) wasdepolymerized. The trial at 350° C. left a slightly tacky residue, butit was not as oily as the residue from the 375° C. trials. Theexperiments run at 300° C. and 325° C. had a solid film left behind withno indication of tackiness or oil. From this set of experiments, itappears that a range of more than about 300° C. to less than about 350°C., and more preferably 325° C. is a temperature at which to run polymerdeposition. The preferred temperature is low enough that polymerbreakdown does not develop. It also provides a fairly high depositionrate that holds steady throughout the run.

[0190] Drum with Block and E-beam (In Block Crucibles)

[0191] The vacuum chamber 112, heater block 118 and rotating drum 114illustrated in FIGS. 11 and 12 are used in this embodiment, along withthe electron beam gun 130.

[0192] To add material, the heater block can be opened and material isloaded into the cavity 128. The drum is covered with PET film. TheE-beam gun is typical of those used in the industry. It has four copperhearths on a rotating plate. One hearth at a time is positioned in linewith the E-beam gun. The material to be evaporated is placed directly inthe hearth or in an appropriate crucible liner that is placed in thehearth at the proper turret location. A second deposition gauge (notshown) is located near the drum surface, above the crucible. It canmeasure the amount of material evaporated from the crucible in angstromsper second (Å/sec). Once this is done, the chamber is closed and thevacuum cycle is started. The chamber is evacuated until the pressuregets to at least 6×10⁻⁵ torr.

[0193] Once the desired vacuum is achieved, power to the three heatersis turned on. The heaters are set to ramp up to the desired temperaturein a 20-minute interval. Measurements are transmitted to a computer fileapproximately every six seconds. The time, block temperature in threezones (° C.), deposition gauge readings (Å/sec), and current vacuumpressure (torr) are documented. Power is supplied to the E-beamapparatus. It is possible to raise the power to the gun in increments of0.1%. The power is raised to a point just below evaporation and allowedto soak or condition. After soaking, the power is raised until thedesired deposition rate is achieved then a shutter is opened once thepolymer begins to deposit. The rotation of the drum is started. Thetrial ends if either the deposition gauge crystal fails or when all ofthe material has been evaporated and the deposition gauge reading fallsto zero. At the end of the trial, the E-beam shutter is closed, the drumrotation is stopped, the power is disconnected from the E-beam, and theblock heater is turned off. After a cool down period, the chamber isopened to atmosphere. The coated material is removed.

[0194] Flake Materials Run in E-Beam

[0195] The following materials were deposited in the E-beam metallizerand were made into flake materials. They were microphotographed asdescribed below and the photographs are shown in the attached Appendix.DEPOSITION RATE Thickness Target METAL (Angstroms/sec) Power (Angstroms)Comments Indium Metal 80 10.6% 475 Silvery Appearance Magnesium Fluoride80 7.9% 475 Very clear film Silicon Monoxide 80 8.6% 475 Brown,Transparent Film Titanium Dioxide 25 10.4% ˜400  Clear, Iridescent FilmZinc Oxide 30 10.9% ˜200  Black residue everywhere Aluminum Oxide 6010.8% 350 Clear, slight iridescence Indium Oxide 60 10.1% 350 SilveryFilm Indium Tin Oxide 60 10.3% 350 Silvery Film Chromium Metal 60 14.0%350 Chrome colored Sandwich of SiO/Al/SiO Silicon Metal 60 12.2% 350Silvery Film Phelly Materials 60 9.8% 350 Copper colored film CopperAlloy Copper (only ran enough to get a vial of flake) Copper coloredflake

EXAMPLES FROM THE ABOVE TABLE Appendix Example 1

[0196] The following construction was made: A roll of 48 gauge polyesterprinted with an thermoplastic release coat was metallized in a Temiscalelectron beam metallizer with indium. The roll was removed from themetallizer and run through a laboratory stripper using acetone toseparate the indium from the polyester. The indium and acetone solutionwas then decanted and centrifuged to concentrate the flakes. Theresulting flakes were than drawn down on a slide and microphotographedon an Image Pro Plus Image Analyzer from Media Cybernetics. The flakesin solution were then reduced in particle size using an IKA Ultra TurexT50 Homogenizer. A particle size distribution was taken on the resultingflake using a Horiba LA 910 laser scattering particle size distributionanalyzer. The particle size reported below are according to thefollowing conventions: D10: 10% of the particles measured are less thanor equal to the reported diameter; D50: 50% of the particles measuredare less than or equal to the reported diameter; D90: 90% of theparticles measured are less than or equal to the reported diameter. Thefinished particle size of the flake was D10=3.3, D50=13.2, D90=31.2.

[0197] The photograph at page 1 of the Appendix illustrates:

[0198] Indium pictured homogenized 30″

[0199] Particle size homogenized 30″ in microns: D10=8.21, D50=26.68,D90=65.18

[0200] Homogenized 6 minutes 30 seconds.

[0201] Finish particle size in microns D10=3.33, D50=13.21, D90=31.32

Appendix Example 2

[0202] The following construction was made: A roll of 48 gauge polyesterprinted with an thermoplastic release coat was metallized in theTemiscal electron beam metallizer with Ti0₂. The roll was removed fromthe metallizer and run through a laboratory stripper using acetone toseparate the Ti0₂ from the polyester. The TiO₂ and acetone solution wasthen decanted and centrifiged to concentrate the flakes. The resultingflakes were than drawn down on a slide and microphotographed on an ImagePro Plus Image Analyzer from Media Cybernetics. The flakes in solutionwere then reduced in particle size using an IKA Ultra Turex T50Homogenizer. A particle size distribution was taken on the resultingflake before and after homogenization using a Horiba LA 910 laserscattering particle size distribution analyzer.

[0203] The photograph at page 2 of the Appendix illustrates:

[0204] TiO₂ pictured “as is” before particle sizing.

[0205] Particle size in microns: D10=16.20, D50=44.17, D90=104.64

[0206] Homogenized 15 minutes.

[0207] Finish particle size in microns D10=7.83, D50=16.37, D90=28.41

Appendix Examples 3 and 4

[0208] The following construction was made: A roll of 48 gauge polyesterprinted with an thermoplastic release coat was metallized in theTemiscal electron beam metallizer with MgF₂. The roll was removed fromthe metallizer and run through a laboratory stripper using acetone toseparate the MgF₂ from the polyester. The MgF₂ and acetone solution wasthen decanted and centrifuged to concentrate the flakes. The resultingflakes were than drawn down on a slide and microphotographed on an ImagePro Plus Image Analyzer from Media Cybernetics. The flakes in solutionwere then reduced in particle size using an IKA Ultra Turex T50Homogenizer. A particle size distribution was taken on the resultingflake before and after homogenization using a Horiba LA 910 laserscattering particle size distribution analyzer.

[0209] The photographs at pages 3 and 4 of the Appendix illustrate:

[0210] MgF₂ pictured “as is” before particle sizing.

[0211] Particle size in microns: D10=16.58, D50=150.34, D90=398.17

[0212] Homogenized 11 minutes.

[0213] Finished particle size in microns D10=0.43, D50=16.95, D90=45.92

Appendix Examples 5 and 6

[0214] The following construction was made: A roll of 48 gauge polyesterprinted with an thermoplastic release coat was metallized in theTemiscal electron beam metallizer with SiO. The roll was removed fromthe metallizer and run through a laboratory stripper using acetone toseparate the SiO from the polyester. The SiO and acetone solution wasthen decanted and centrifuged to concentrate the flakes. The resultingflakes were than drawn down on a slide and microphotographed on an ImagePro Plus Image Analyzer from Media Cybernetics. The flakes in solutionwere then reduced in particle size using an IKA Ultra Turex T50Homogenizer. A particle size distribution was taken on the resultingflake before and after homogenization using a Horiba LA 910 laserscattering particle size distribution analyzer.

[0215] The photographs at pages 5 and 6 of the Appendix illustrate:

[0216] SiO pictured “as is” before particle sizing.

[0217] Particle Size in microns: D10=17.081, D50=67.80, D90=188.31

[0218] Homogenized 17 minutes.

[0219] Finished particle size in microns: D10=5.75, D50=20.36, D90=55.82

Appendix Examples 7, 8 and 9

[0220] The following construction was made: A roll of 48 gauge polyesterprinted with an thermoplastic release coat was metallized in theTemiscal electron beam metallizer with ZnO The roll was removed from themetallizer and run through a laboratory stripper using acetone toseparate the ZnO from the polyester. The ZnO and acetone solution wasthen decanted and centrifuged to concentrate the flakes. The resultingflakes were than drawn down on a slide and microphotographed on an ImagePro Plus Image Analyzer from Media Cybernetics. The flakes in solutionwere then reduced in particle size using an IKA Ultra Turex T50Homogenizer. A particle size distribution was taken on the resultingflake before and after homogenization using a Horiba LA 910 laserscattering particle size distribution analyzer.

[0221] The photographs at pages 7, 8 and 9 of the appendix illustrate:

[0222] ZnO pictured “as is” before particle sizing.

[0223] Particle size in microns: D10=23.58, D50=63.32, D90=141.59

[0224] Finished particle size in microns: D10=7.69, D50=18.96, D90=38.97

Appendix Examples 10, 11 and 12

[0225] The following construction was made: A roll of 48 gauge polyesterprinted with an thermoplastic release coat was metallized in theTemiscal electron beam metallizer with Al₂O₃. The roll was removed fromthe metallizer and run through a laboratory stripper using acetone toseparate the Al₂O₃ from the polyester. The Al₂O₃ and acetone solutionwas then decanted and centrifuged to concentrate the flakes. Theresulting flakes were than drawn down on a slide and microphotographedon an Image Pro Plus Image Analyzer from Media Cybernetics. The flakesin solution were then reduced in particle size using an IKA Ultra TurexT50 Homogenizer. A particle size distribution was taken on the resultingflake before and after homogenization using a Horiba LA 910 laserscattering particle size distribution analyzer.

[0226] The photographs at pages 13 and 14 of the appendix illustrate:

[0227] Al₂O₃ pictured “as is” before particle sizing.

[0228] Particle Size in microns: D10=6.37, D50=38.75, D90=99.94

[0229] Homogenized 9 minutes.

[0230] Finished particle size in microns: D10=1.98, D50=16.31,D90=39.77)

Appendix Examples 13 and 14

[0231] The following construction was made: A roll of 48 gauge polyesterprinted with an thermoplastic release coat was metallized in theTemiscal electron beam metallizer with In₂O₃. The roll was removed fromthe metallizer and ran through a laboratory stripper using acetone toseparate the In₂O₃ from the polyester. The In₂O₃ and acetone solutionwas then decanted and centrifuged to concentrate the flakes. Theresulting flakes were than drawn down on a slide and microphotographedon an Image Pro Plus Image Analyzer from Media Cybernetics. The flakesin solution were then reduced in particle size using an IKA Ultra TurexT50 Homogenizer. A particle size distribution was taken on the resultingflake before and after homogenization using a Horiba LA 910 laserscattering particle size distribution analyzer.

[0232] The photographs at pages 13 and 14 of the Appendix illustrate:

[0233] In₂O₃ Pictured “as is” before particle sizing.

[0234] Particle size in microns: D10=18.88, D50=50.00, D90=98.39

[0235] Homogenized 3 minutes.

[0236] Finished particle size in microns: D10=8.89, D50=20.22, D90=38.92

[0237] Relative Refractive Index used: 2.64-2.88

Appendix Examples 15, 16 and 17

[0238] The following construction was made: A roll of 48 gauge polyesterprinted with an thermoplastic release coat was metallized in theTemiscal electron beam metallizer with indium tin oxide (ITO). The rollwas removed from the metallizer and run through a laboratory stripperusing acetone to separate the ITO from the polyester. The ITO andacetone solution was then decanted and centrifuged to concentrate theflakes. The resulting flakes were then drawn down on a slide andmicrophotographed on an Image Pro Plus Image Analyzer from MediaCybernetics. The flakes in solution were than reduced in particle sizeusing an IKA Ultra Turex T50 Homogenizer. A particle size distributionwas taken on the resulting flake before and after homogenization using aHoriba LA 910 laser scattering particle size distribution analyzer.

[0239] The photographs at pages 15, 16 and 17 illustrate:

[0240] ITO pictured “as is” before particle sizing.

[0241] Particle size in microns: D10=21.70, D50=57.00, D90=106.20

[0242] Homogenized 6 minutes.

[0243] Finished particle size in microns: D10=10.40, D50=20.69,D90=36.32

Appendix Examples 18, 19, 20 and 21

[0244] The following construction was made: A roll of 48 gauge polyesterprinted with an thermoplastic release coat was metallized in theTemiscal electron beam metallizer with Si. The roll was removed from themetallizer and run through a laboratory stripper using acetone toseparate the Si from the polyester. The Si and acetone solution was thendecanted and centrifuged to concentrate the flakes. The resulting flakeswere then drawn down on a slide and microphotographed on an Image ProPlus Image Analyzer from Media Cybernetics. The flakes in solution werethan reduced in particle size using an IKA Ultra Turex T50 Homogenizer.A particle size distribution was taken on the resulting flake before andafter homogenization using a Horiba LA 910 laser scattering particlesize distribution analyzer.

[0245] The photographs at Appendix pages 18, 19, 20 and 21 illustrate:

[0246] Si pictured “as is” before particle sizing.

[0247] Particle size in microns: D10=20.20, D50=57.37, D90=140.61

[0248] Homogenized 20 minutes.

[0249] Finished particle size in microns: D10=11.9, D50=27.0, D90=55.5

[0250] The following construction was made: A roll of 48 gauge polyesterprinted with an thermoplastic release coat was metallized in theTemiscal electron beam metallizer with a sandwich of SiO,Al,SiO The rollwas removed from the metallizer and run through a laboratory stripperusing acetone to separate the Sandwich from the polyester. TheSiO,Al,SiO and acetone solution was then decanted and centrifuged toconcentrate the flakes. The resulting flakes were then drawn down on aslide and microphotographed on an Image Pro Plus Image Analyzer fromMedia Cybernetics. The flakes in solution were than reduced in particlesize using an IKA Ultra Turex T50 Homogenizer. A particle sizedistribution was taken on the resulting flake before and afterhomogenization using a Horiba LA 910 laser scattering particle sizedistribution analyzer.

[0251] The photographs at Appendix pages 22 and 23 illustrate:

[0252] SiO Al SiO sandwich pictured “as is” before particle sizing

[0253] Particle size in microns: D10=29.7, D50=77.6, D90=270.2

Appendix Examples 24 and 25

[0254] The following construction was made: A roll of 48 gauge polyesterprinted with an thermoplastic release coat was metallized in theTemiscal electron beam metallizer with chromium The roll was removedfrom the metallizer and run through a laboratory stripper using acetoneto separate the chromium from the polyester. The chromium and acetonesolution was then decanted and centrifuged to concentrate the flakes.The resulting flakes were then drawn down on a slide andmicrophotographed on an Image Pro Plus Image Analyzer from MediaCybernetics. The flakes in solution were than reduced in particle sizeusing an IKA Ultra Turex T50 Homogenizer. A particle size distributionwas taken on the resulting flake before and after homogenization using aHoriba LA 910 laser scattering particle size distribution analyzer.

[0255] The photographs at Appendix pages 24 and 25 illustrate:

[0256] Chromium pictured “as is” before particle sizing

[0257] Particle size in microns: D10=13.1, D50=8.9, D90=59.8

[0258] Homogenized 3 minutes

[0259] Finished particle size in microns: D10=9.82, D50=19.81; D90=37.55

Appendix Example 26

[0260] The following construction was made: A roll of 48 gauge polyesterprinted with an thermoplastic release coat was metallized in theTemiscal electron beam metallizer with an M-401 copper, zinc, silveralloy, Phelly Materials, Emerson, N.J. The roll was removed from themetallizer and run through a laboratory stripper using acetone toseparate the alloy from the polyester. The alloy and acetone solutionwas then decanted and centrifuged to concentrate the flakes. Theresulting flakes were then drawn down on a slide and microphotographedon an Image Pro Plus Image Analyzer from Media Cybernetics. The flakesin solution were than reduced in particle size using an IKA Ultra TurexT50 Homogenizer. A particle size distribution was taken on the resultingflake before and after homogenization using a Horiba LA 910 laserscattering particle size distribution analyzer.

[0261] The photograph at Appendix page 26 illustrates:

[0262] Alloy pictured “as is” before particle sizing

[0263] Particle size in microns: D10=69.6, D50=161.2, D90=313.4

[0264] Homogenized 20 minutes

[0265] Finished particle size in microns: D10=13.32, D50=27.77,D90=51.28

[0266]FIGS. 13 and 14 show a vacuum chamber, rotating drum and polymervapor chamber similar to FIGS. 11 and 12, except that the polymer isdelivered to the chamber by a wire feed mechanism 136 described in moredetail below. In this embodiment, the heater block has small holes inboth ends that allow a coated wire 143 to pass into the heated slotarea. The coated wire is unwound from a spool 164 and advanced at apredetermined rate through the block where the polymer is evaporatedinto the slot area then the spent wire is rewound on a second spool 166.The slot is open into a cavity running through the center of the block.In this embodiment, the area around the heater block and drum is pumpedto selectively cool that area for condensing the polymers coated on thewire. This prevents escape of vapor toward the E-beam area of thechamber.

Appendix Example 27

[0267] Example: Drum with Polymer Block and E-Beam (Wire Feed) ReleaseMaterial Styron Support Material Aluminum Supplier Dow Supplier Mat.Research Corp. No. 685D No. 90101E-AL000-30002 PVD Conditions: ReleaseE-Beam Thickness Support Drum Wire Coat Wire Power (Angstroms) ThicknessSpeed Revolutions Size Weight Speed 15% 200 150 Angstroms 1 RPM 1000.005 in./dia 0.0005 6 grams/in.

[0268] The following construction was made at the conditions shownabove: 48 gauge polyester wrapped around the drum for easy removal waspolymer release coated with styrene and metallized in the Temiscalelectron beam metallizer with aluminum. The polyester film was removedfrom the metallizer and run through a laboratory releasing device usingacetone to separate the Aluminum from the releasing layers and thepolyester film. The aluminum and acetone solution was then decanted andcentrifuged to concentrate the flakes. The resulting flakes were thandrawn down on a slide and microphotographed on an Image Pro Plus ImageAnalyzer from Media Cybernetics. The flakes in solution were thenreduced in particle size using an IKA Ultra Turex T50 Homogenizer. Aparticle size distribution was taken on the resulting flake using aHoriba LA 910 laser scattering particle size distribution analyzer.

[0269] The photographs at page 27 of the Appendix illustrates:

[0270] Starting Particle size

[0271] D10=13.86, D50=34.65, D90=75.45.

[0272] Homogenized.

[0273] Finished particle size in microns D105.10, D50=13.19, D90=25.80

Appendix Example 28

[0274] Example: Drum with Polymer Block and E-Beam (Wire Feed) SiliconeRelease Material Styron Support Material Dioxide Supplier Dow SupplierCerac No. 685D No. S-1060 PVD Conditions: Release E-Beam ThicknessSupport Drum Wire Coat Wire Power (Angstroms) Thickness SpeedRevolutions Size Weight Speed 8% 200 200 Angstroms 1 RPM 100 0.005in./dia 0.0005 6 grams/in.

[0275] The following construction was made at the conditions shownabove: 48 gauge polyester wrapped around the drum for easy removal waspolymer release coated with styrene and metallized in the Temiscalelectron beam metallizer with Silicone Monoxide. The polyester film wasremoved from the metallizer and run through a laboratory releasingdevice using acetone to separate the Silicon Monoxide from the releasinglayers and the polyester film. The silicon monoxide and acetone solutionwas then decanted and centrifuged to concentrate the flakes. Theresulting flakes were then drawn down on a slide and microphotographedon an Image Pro Plus Image Analyzer from Media Cybernetics.

[0276] The flakes are shown in the photograph in Appendix page 28.

Appendix Example 29

[0277] Example: Drum with Polymer Block and E-Beam (Wire Feed) MagnesiumRelease Material Styron Support Material Fluoride Supplier Dow SupplierCerac No. 685D No. M-2010 PVD Conditions: Release E-Beam ThicknessSupport Drum Wire Coat Wire Power (Angstroms) Thickness SpeedRevolutions Size Weight Speed 7.5% 200 200 Angstroms 1 RPM 1000.005in./dia 0.0005 6 grams/in

[0278] The following construction was made at the conditions shownabove: 48 gauge polyester wrapped around the drum for easy removal waspolymer release coated with styrene and metallized in the Temiscalelectron beam metallizer with magnesium fluoride. The polyester film wasremoved from the metallizer and run through a laboratory releasingdevice using acetone to separate the magnesium fluoride from thereleasing layers and the polyester film.

[0279] The magnesium fluoride and acetone solution was then decanted andcentrifuged to concentrate the flakes. The resulting flakes were thandrawn down on a slide and microphotographed on an Image Pro Plus ImageAnalyzer from Media Cybernetics.

[0280] The flakes are shown in the photograph at Appendix page 29.

[0281] Drum with Vapor Tube and E-beam (Wire Feed)

[0282]FIGS. 15, 1615A and 16A show two separate embodiments of a wirefeed mechanism for delivering coated polymer to a vacuum chamber whichincludes a rotating drum, a deposition gauge, a polymer vapor tube witha coated polymer coated wire feed system, and an electron beam (E-beam)gun. The drum is as described previously. The vapor tube is equippedwith a heated polymer vapor path surrounded by a water-cooled tubeseparated by a vacuum gap. A slot in the tubes allows the evaporatedpolymer to pass through to the drum surface. The vapor tube produces adifferential pressure area adjacent the heater block and drum forpreventing escape of vapor to the E-beam area of the chamber. In theembodiment shown in FIGS. 15 and 16, the wire feed housing contains awire supply spool and a take-up spool. The wire is unwound and coatedwith polymer and runs around the heater block. Polymer is evaporatedfrom the coated wire and is directed onto the drum surface. The end viewof FIG. 16 shows the outer tube with its slot facing the drum. The outertube is cooled and the vapor tube inside is heated. This view also showsthe heater block with the wire wrap. The wire passes into the vaportube, around the heated tube and back out to the take-up spool.

[0283] The embodiment of FIGS. 15 and 16 shows a vacuum chamber 132 andheater block 134 similar to those previously described, except thatpolymer for the release layers is fed into the vacuum chamber via thecoated wire feed apparatus 136. The vacuum chamber includes a rotatingdrum 128, a deposition gauge 140 and an electron beam (E-beam) gun 142.As mentioned previously, the drum is approximately one foot in diameterand six inches wide on the surface. It can rotate at a maximum speed oftwo rotations per minute. The heater block 134 comprises a heatedpolymer vapor chamber 144 which is cylindrical in shape with a slot 145carved into one area. The heated inner tube is shown at 146. The wirefeed apparatus 136 includes an elongated housing 147 containing a wire148 which is coated with polymer and then fed into the heater block. Thewire wraps around a heated shoe 149. The wire feed apparatus alsoincludes a turbo pump 150, an ion gauge and a thermocouple gauge 154.The coated wire is unwound from a spool 156 and advanced at apredetermined rate through the heater block where the polymer isevaporated into the slot area 158 and then the spent wire is rewound ona second spool 160. The slot is open into a cavity running through thecenter of the heater block. The pump assists in delivering vaporizedpolymer to the drum surface. The heater block has three independentheaters that can be used to control the temperature of the block. Thedeposition gauge 140 is placed approximately one inch in front of theslot. It can measure the amount of material passing through the slot inangstroms per second (Å/sec).

[0284] In use, the drum is covered with PET film. The wire feedmechanism and heater block are used to coat a layer of polymeric releasematerial on the carrier, followed by activating the E-beam gun to coat alayer of metal or other material on the release coat, and so on. TheE-beam gun 142 is typical of those used in the industry. It has fourcopper hearths on a rotating plate. One hearth at a time is positionedin line with the E-beam gun. The material to be evaporated is placeddirectly in the hearth or in an appropriate crucible liner that isplaced in the hearth at the proper turret location. A second depositiongauge (not shown) is located near the drum surface, above the crucible.It can measure the amount of material evaporated from the crucible inangstroms per second (Å/sec). Once this is done, the chamber is closedand the vacuum cycle is started. The chamber is evacuated until thepressure gets to at least 6×10⁻⁵ torr.

[0285] Once the desired vacuum is achieved, power to the three heatersis turned on. The heaters are set to ramp up to the desired temperaturein a 20-minute interval. Measurements are transmitted to a computer fileapproximately every six seconds. The time, block temperature in threezones (° C.), deposition gauge readings (Å/sec), and current vacuumpressure (torr) are documented. Power is supplied to the E-beamapparatus. It is possible to raise the power to the gun in increments of0.1%. The power is raised to a point just below evaporation and allowedto soak or condition. After soaking, the power is raised until thedesired deposition rate is achieved then a shutter is opened and thepolymer coated wire mechanism is set to the desired rate and depositionof polymer begins. The rotation of the drum is started. At the end ofthe trial, the E-beam shutter is closed, the drum rotation is stopped,the power is disconnected from the E-beam, the block heater and wirefeed is turned off. After a cool down period, the chamber is opened toatmosphere. The coated material is removed.

[0286] In the embodiment shown in FIGS. 15A and 16A, the vapor tube hassmall holes in both ends that allow the coated wire 162 to pass into aheated block in the vapor tube. The coated wire is unwound from a firstspool 164 and advanced at a predetermined rate through the tube wherethe polymer is evaporated into the slot area 158 and then the spent wireis rewound on a second spool 166. The vapor tube walls are heated bystrip heaters and the block has an independent heater that can be usedto control the temperature of the system. A deposition gauge 168 isplaced approximately one inch in front of the slot. It can measure theamount of material passing through the slot in angstroms per second(Å/sec).

[0287] The drum is covered with PET film. The E-beam gun has four copperhearths on a rotating plate. One hearth at a time is positioned in linewith the E-beam gun. The material to be evaporated is placed directly inthe hearth or in an appropriate crucible liner that is placed in thehearth at the proper turret location. A second deposition gauge (notshown) is located near the drum surface, above the crucible. It canmeasure the amount of material evaporated from the crucible in angstromsper second (Å/sec). Once this is done, the chamber is closed and thevacuum cycle is started. The chamber is evacuated until the pressuregets to at least 6×10⁻⁵ torr. Once the desired vacuum is achieved, powerto the tube and block heaters is turned on. The heaters are set to rampup to the desired temperature in a 20-minute interval. Measurements aretransmitted to a computer file approximately every six seconds. Thetime, block temperature in three zones (° C.), deposition gauge readings(Å/sec), and current vacuum pressure (torr) are documented. Power issupplied to the E-beam apparatus. It is possible to raise the power tothe gun in increments of 0.1%. The power is raised to a point just belowevaporation and allowed to soak or condition. After soaking, the poweris raised until the desired deposition rate is achieved then a shutteris opened and the polymer coated wire mechanism is set to the desiredrate and deposition of polymer begins. The rotation of the drum isstarted. At the end of the trial, the E-beam shutter is closed, the drumrotation is stopped, the power is disconnected from the E-beam, thetube, block heater and wire feed is turned off. After a cool downperiod, the chamber is opened to atmosphere. The coated material isremoved.

Appendix Example 30

[0288] Example: Drum with Vapor Tube and E-Beam (Wire Feed) ReleaseMaterial Styron Support Material Aluminum Supplier Dow Supplier Mat.Research No. 685D No. 90101E-AL000-30002 PVD Conditions: Release E-BeamThickness Support Drum Wire Coat Wire Power (Angstroms) Thickness SpeedRevolutions Size Weight Speed 20% 200 150 Angstroms 1 RPM 100 0.005in./dia 0.0005 6 grams/in.

[0289] The following construction was made at the conditions shownabove: 48 gauge polyester wrapped around the drum for easy removal waspolymer release coated with styrene and metallized in the Temiscalelectron beam metallizer with aluminum. The polyester film was removedfrom the metallizer and run through a laboratory releasing device usingacetone to separate the aluminum from the releasing layers and thepolyester film. The aluminum and acetone solution was then decanted andcentrifuged to concentrate the flakes. The resulting flakes were drawndown on a slide and microphotographed on an Image Pro Plus ImageAnalyzer from Media Cybernetics. The flakes in solution were thenreduced in particle size using an IKA Ultra Turex T50 Homogenizer. Aparticle size distribution was taken on the resulting flake using aHoriba LA 910 laser scattering particle size distribution analyzer. Thefinished particle size of the flake was D10=3.3, D50=13.2, D90=31.2.

[0290] The photograph at page 30 of the Appendix illustrates:

[0291] Aluminum pictured homogenized 30″

[0292] Particle size homogenized 30″ in microns: D10=8.21, D50=26.68,D90=65.18

[0293] Homogenized 6 minutes 30 seconds.

[0294] Finish particle size in microns D10=3.33, D50=13.21, D90=31.32

[0295] Example: Drum with Vapor Tube and E-Beam (Wire Feed)Nanoparticles Release Material Styron Support Material Aluminum SupplierDow Supplier Mat. Research No. 685D No 90101E-AL000-30002 PVDConditions: Release B-Beam Thickness Support Drum Wire Coat Wire Power(Angstroms) Thickness Speed Revolutions Size Weight Speed 17% 200 3Angstroms 2.2 RPM 100 0.005 in./dia 0.0005 6 grams/in.

[0296] The following construction was made at the conditions shownabove: 48 gauge polyester wrapped around the drum for easy removal waspolymer release coated with styrene and metallized in the Temiscalelectron beam metallizer with aluminum. The polyester film was removedfrom the metallizer and run through a laboratory releasing device usingacetone to separate the aluminum from the releasing layers and thepolyester film. The resulting aluminum particle slurry was saved in avial for further study.

[0297] The goal of the trial was to achieve nanoparticles of aluminumresulting from managing the deposition process such that as the aluminumis deposited on the releasing layer it remains in the Island growthstate. These islands ofuncoalesced aluminum are then coated withreleasing material then recoated with islands of aluminum. This isrepeated until a 100 multilayer sandwich of release/aluminumislands/release is formed.

[0298] Drum with Polymer Block & E-Beam (Melt Pump Extruder)

[0299] Referring to FIGS. 17 and 18, a vacuum chamber and heater blocksimilar to those described above is modified to deliver molten polymer(thermoplastic polymer used as a release coat material) to the vacuumchamber. The vacuum chamber includes the rotating drum 168, a depositiongauge, the stainless steel heater block 170, and an electron beam(E-beam) gun 172. The drum is approximately one foot in diameter and sixinches wide on the surface. The drum can be rotated and the speed andnumber of revolutions monitored. The heater block slot is open into acavity running through the center of the block. The block has threeindependent heaters used to control the temperature of the block. Theblock is fed molten polymer by two heated capillary tubes 174 connectedto the polymer crucibles located in each end or the block. These tubesare connected to a melt pump located outside of the chamber. It is fedby a nitrogen blanketed melt vessel 175 containing conditioned polymerand an extruder 176. A deposition gauge placed approximately one inch infront of the slot measures the amount of material passing through theslot in angstroms per second (Å/sec).

[0300] To add material, polymer is pumped to cavities in each end of theheater block. The drum is covered with PET film. The E-beam gun has fourcopper hearths on a rotating plate. One hearth at a time is positionedin line with the E-beam gun. The material to be evaporated is placeddirectly in the hearth or in an appropriate crucible liner placed in thehearth at the proper turret location. A second deposition gauge islocated near the drum surface, above the crucible. It measures theamount of material evaporated from the crucible in angstroms per second(Å/sec). Once this is done, the chamber is closed and the vacuum cycleis started. The chamber is evacuated until the pressure reaches at least6×10⁻⁵ torr. Once the desired vacuum is achieved, power to the threeheaters is turned on. The heaters are set to ramp up to the desiredtemperature in a 20 minute interval. Measurements are transmitted to acomputer file approximately every 6 seconds. The time, block temperaturein three zones (° C.), deposition gauge readings (Å/sec), and currentvacuum pressure (torr) are documented. Power is supplied to the E-beamapparatus. It is possible to raise the power to the gun in increments of0.1%. The power is raised to a point just below evaporation and allowedto soak or condition. After soaking, the power is raised until thedesired deposition rate is achieved and then a shutter is opened oncethe polymer begins to deposit. Rotation of the drum is started and themelt pump is set to the desired rate. The trial ends if either thedeposition gauge crystal fails or when all of the material has beenevaporated and the deposition gauge reading falls to zero. At the end ofthe trial, the E-beam shutter is closed, drum rotation is stopped, themelt pump is stopped, the power is disconnected from the E-beam, and theblock heater is turned off. After a cool down period, the chamber isopened to atmosphere. The coated material is removed.

[0301] Release-coated Carrier Film Process

[0302] In one embodiment, the present invention can be used formanufacturing release-coated polymeric carrier film such asrelease-coated polyester (PET). Referring to FIG. 19, a polyestercarrier film 180 is wrapped around a rotating cooling drum 182 containedin a vacuum chamber 184. The film passes from a film unwind station 186around approximately 300° C. or more of surface area of the rotatingcooling drum, and the coated film is then taken up at a film rewindstation 188. A polymer delivery source 190 directs the polymer materialtoward the carrier film and the E-beam 192 gun vaporizes the polymer forcoating it onto the carrier film. The polymeric coating hardens and isthen taken up at the rewind station. The process provides athermoplastic polymeric release-coated heat-resistant polymeric carrierfilm, in which the film provides good release properties for flakematerial applied to the film by vapor deposition techniques in a vacuumchamber. The film provides effective release in forming thin flatangstrom level flakes.

[0303] Polystyrene Trials

[0304] From trials in the electron beam metallizer, it was discoveredthat the heater block temperature had a significant effect on thecondition of the polystyrene after it was evaporated and deposited. Forall trials, the Dow 685D polystyrene was used as deposition material.This material has a molecular weight (MW) of roughly 300,000.

[0305] Trials were run with heater block temperatures ranging from 300°C. to 375° C. in 25° C. increments. The rate at which the block washeated was varied, but did not seem to have as significant effect as theeventual temperature. All trials were run according to the Drum withBlock Procedure described above.

[0306] In the first trial, the block was loaded with 10 pellets of theDow 685D polystyrene. The temperatures on the heaters were set for 300°C. At that temperature, there is minimal deposition. Gauge readingsranged from 5-10 Å/sec. At the end of the trial there was very littleapparent residue.

[0307] In the next trial, the block was set to reach a temperature of325° C. Deposition increased into the 20-30 Å/sec range. At the end ofthe trial, there was a noticeable film deposited. The film was clear incolor and was solid with no tackiness.

[0308] Next the block was programmed to reach 350° C. The depositionrates were similar to that in the trial to 325° C. At the end of thetrial, the film was different than the film that was formed in theprevious trial. The film in this trial was tackier to the touch andthere appeared to be a slight discoloration.

[0309] Finally, the block was set for a temperature ramp to 375° C.Deposition rates increased to a rate of nearly 40 Å/sec. At the end ofthe trial, yellowish oil was left on the film. The oil was easily wipedaway, but there was no sign of clear polystyrene film beneath it.

[0310] From these trials it was concluded that above 350° C. polystyrenebegins to degrade. This confirms values that were found in theliterature. At temperatures greater than 350° C., the polystyreneevaporates and then appears to depolymerize and leave a residue ofnearly pure styrene monomer. This was confirmed by FTIR analysis of theresidue.

[0311] In further study, samples of the Dow polystyrene were sent to anoutside lab for analysis. A method was devised to determine what wasevaporating from the polymer as the temperature was raised to a desiredoperating temperature. Using a “Direct Insertion Probe” method coupledwith GC-MS analysis, the temperature was set to ramp to 325° C. at arate of 30° C./min. Once the maximum temperature was reached, it washeld for 10 minutes.

[0312] An ion counter in the apparatus indicated when material was beingevaporated from the solid pellet. Two peaks appeared during the trial,one at approximately 260° C. and another at 325° C. GC-MS analysis wasperformed on these two peaks. The first peak showed large concentrationsof low molecular weight species including, but not limited to, monomersand dimers of polystyrene. The second peak does not show nearly as manyvolatiles in its GC-MS analysis. From this analysis it was concludedthat upon first heating, a large quantity of unpolymerized material andmany other low molecular weight volatiles are liberated from the bulkpolystyrene. After prolonged heating, the desired polymer is evaporatedand deposited onto the desired surface. I was concluded that for optimumperformance, the bulk polymer needs to be preheated or otherwiseconditioned to remove as much “low end” material as possible.

[0313] In another experiment, we used the same Direct Insertion Probemethod to try to gain further insight into what is happening in thefirst peak seen in the first experiment. In this trial the applied heatwas ramped up to 260° C. and held the temperature. This is where thepeak appeared in the first trial. The purpose was to characterize whatwas being evaporated at this point by GC-MS and also see if the materialcould be removed from the bulk material by a preheating step.

[0314] The peak appeared in approximately the same place and GC-MSshowed a large assortment of low molecular weight species. Theseincluded some trace of the styrene monomer, but there were numerousother organic fragments present. After a period of about 10-12 minutes,the peak had disappeared. This indicated that the volatile material hadbeen removed from the bulk material and a strategy of preheating shouldbe effective in forming clean polymer films.

[0315] From this series of tests new procedures were developed toincrease the effectiveness of depositing polystyrene film with the Dow685D polymer. First, the bulk material is heated to a temperature of260-300° C. During this preheating, the film should be covered so as notto allow the low end products to reach the web. This step may also bedone outside the vacuum or at least outside of the deposition chamber sothat contamination can be minimized. After sufficient time, thetemperature should then be raised to 325° C. This temperature providesthe highest deposition rate without causing degradation of thepolystyrene.

[0316] Further observations came from running similar experiments withother polystyrene samples. In this case we used a 4,000 MW and a 290,000MW polystyrene supplied by Pressure Chemical. These samples arepolystyrene standards and have very narrow molecular weightdistributions. They are also free of most contaminants that would befound in most commercial polymers. From these experiments we made thefollowing conclusions. The use of the 4,000 MW material has less of animpact on the vacuum pressure than the 290,000 MW material. The pressurerises more when the higher molecular weight material is used. This isconsistent with data we found during trials in the bell jar. We alsoobserved that the 290,000 MW material began deposition at a lowertemperature than the 4,000 MW material. We confirmed this by runningTGAs on both materials. The TGAs showed that the 4,000 MW material doesindeed show a weight loss beginning at a higher temperature than thatobserved for the 290,000 MW polymer.

[0317] Polymer Conditioning

[0318] Before the polymer can be used in a deposition process, it mustbe conditioned to remove moisture and low molecular weight material fromthe bulk polymer. Using the Dow 685D polystyrene, we accomplished thisin a two stage conditioning process. In the first stage, a quantity ofthe polystyrene is placed in a vacuum oven and held at 225° C. for 16hours. This temperature is high enough to drive off most moisture in thepolymer. This temperature is also chosen because it is below the pointwhere polymer degradation is seen. In trials run at 275° C., thepolystyrene sample showed significant degradation after the 16 hourconditioning period. After the conditioning period, the polymer isremoved and placed in a desiccator so that it does not take on anymoisture while it is cooling.

[0319] The second stage of the conditioning is done when the polymer isready to be used in the metallizer. It is removed from the desiccatorand immediately placed in the metallizer so that moisture gain isminimized. Before deposition begins, the polymer block containing thefirst stage conditioned polymer is heated to 275° C. and held at thattemperature for 20 minutes. At this temperature, any remaining moistureis driven off and the low molecular weight material in the polymer isalso removed. This low molecular weight material will include unreactedmonomer and many other impurities found in the bulk polystyrene. Afterholding at 275° C. for the necessary conditioning time, the polymershould be ready for deposition.

[0320] By utilizing this two stage conditioning process, the final filmshould be of a consistent molecular weight and it should also be free ofmost low molecular weight impurities. This should provide for a muchmore consistent and reliable film.

[0321] Reuse of Solvent & Polymer

[0322] When the current release coat is stripped and the flake iscollected the spent solvent along with the dissolved release coat issent through a distillation process to reclaim the solvent. When thesolvent is reclaimed the still bottoms are sent out to be disposed of ashazardous waste. In this experiment we attempted to reuse the stillbottoms as a release coat. The still bottoms as collected were 24% NVM.This material was reduced to 8.3% NVM with three parts IPAC and one partNPAC. This lacquer was than drawn down on 2 mil polyester using a #2Meyer rod. The resulting coating was clear with a coat weight of 0.3grams per meter square. The draw down was than metallized with aluminumin the bell jar metallizer. The resulting aluminum layer had an opticaldensity of 2 to 2.5 as measured on the Macbeth densitometer.

[0323] The resulting construction was than dissolved in acetone taking30 seconds to release from the polyester. The flake was than drawn downon a slide and analyzed. Flake produced by this method was in the 400 to600 micron range with a smooth surface and was indistinguishable fromthe current product.

[0324] Wire Coating

[0325]FIG. 20 illustrates a wire coating apparatus for coating polymeronto the wire used in the wire feed embodiments described previously.

[0326] Materials:

[0327] A mixture of fully dissolved Dow 685 polystryene polymer inxylene. Dow 685 45 pts by wt Xylene 55 pts by wt

[0328] Bare Nickel/Chromium wire 0.005 inch in gage from ConsolidatedElectronic Wire and Cable.

[0329] Description of Apparatus:

[0330] Referring to FIG. 20, the coating apparatus consists of foursections: unwind 200, coating body 202, drying tube 204, and winder 206.The spool of wire is restricted in side to side movement while allowingit to unwind with a minimum of resistance. The coating body comprises asyringe body 208, Becton Dickson 5 cc disposable syringe, and a syringeneedle 210, Becton Dickson 20GI Precision Glide needle. The disposablesyringe is filled with the coating mixture and the needle meters a givenamount of material onto the wire. The drying tube is constructed fromcopper plumbing tubing. From top to bottom the tube consists of a ½ inchtube 212 six inches long, a ½ to ¾ reducer 214, a ¾ inch tube 216 twoinches long, a ¾ inch tee 218 from which a 4 inch ¾ inch tube 220extends perpendicularly. An exhaust fan 222 is attached to this pipedrawing air from the apparatus. The straight section of the tee isattached to a {fraction (3/4)} inch copper tube 224 five feet long. Thissection is the drying section of the apparatus. Another ¾ inch tee 226is attached to the 5 foot section. The perpendicular tee is attached toa three inch ¾ inch tube 228 connected to a 90 degree elbow 230 turnedupwards. To this elbow is attached a 1½ inch tube 232 and a ¾ inchthreaded connecter 234. This connecter is attached to a two inch to ¾inch black iron reducer. A two inch pipe 236 five inches long is screwedinto this reducer. The two inch pipe holds the barrel of the hot airgun. The vertical section of the tee is attached to a two inch ¾ inchtube 238, then reduced at 240 to ½ inch. A final six inch section of ½inch tubing 242 is attached.

[0331] Description of coating application:

[0332] Using the apparatus displayed above the coating is applied to thewire. The wire is unwound from the spool and fed though a syringe bodythat contains the mixture of polystyrene polymer and solvent. As thewire is drown down the syringe body through the syringe needle the wireis covered with the mixture. The coated wire is fed through a coppertube through which heated air is passed. Air is drawn from an exit portin the top of the tube at a rate greater than heated air is suppliedfrom a port in the bottom of the tube. The extra air required by theexhaust port is supplied at the ends of the tube where the wire entersand exits. The amount of hot air supplied to the tube was controlledthrough the use of a rheostat. It was found 85% of full output was thepreferred temperature. Greater temperature caused the coating toblister, less temperature detracted from drying. The wire was wound on aspool after passing through the drying tube. The desired rate of thewire was 22 inches per minute through the drying tube. The speed of thewinding spool was controlled manually using another rheostat. As morewire was wound onto the spool the rheostat setting was dropped tocompensate for the faster pull of the wire during winding. Final coatingon the wire was in the 0.4 to o.5 mg/inch range.

[0333] Dow Styron 685D

[0334] Sample Preparation and Analysis

[0335] About 75 milligrams of the polystyrene resin from each plasticcontainer was separately dissolved in 10 mL of tetrahydrofuran (THF) andtumbled for about 3 hours. Each THF solution was filtered through 0.45μm PTFE filter and placed in an autosampler vial.

[0336] The GPC instrument was a Waters 2690 pumping system with a Waters410 refractive index detector. The columns were three Plgel Mixed-C 300mm×7.5 from Polymer Labs. The mobile phase was THF at 1.0 mL/min. Theinjection size was 50 μL. Calibration was against a set of twelvepolystyrene standards obtained from Polymer Labs, ranging from 580 to1,290,000 Da. Millennium version 3.2 software from Waters was used withthe GPC option. Calibration was done daily and a check sample of SRM 706polystyrene from the National Institute for Standards and Technology wasalso analyzed daily with each batch of samples.

[0337] Results

[0338] The calculated value for the molecular weight distribution of thesoluble polymer portion of the sample is shown in the following table.The values for the peak molecular weight (Mp), number average molecularweight (Mn) and weight average molecular weight (Mw) are expressed asthousands to give the correct number of significant figures. Qualitycontrol data indicate that a relative difference of ten percent for Mnand five percent for Mw are not significant. Sample Mp Mn Mw DispersitySTYRON 685 D 266 k 107 k 313 k 2.94 STYRON 685 D duplicate 272 k 138 k320 k 2.32 STYRON 685 D average 269 k 123 k 317 k 2.63

[0339] Polystyrene Polymer Characterization Data from Pressure ChemicalCo. Nominal 290,000 MW Styrene By Lalls: M_(w) = 287,000 By SizeExclusion Chromatography: M_(w) = 288,800 1 × 60 cm Pigel 5 micron mixedgel M_(n) = 274,600 THF @ 1 ml/min. 20 ml. @ 0.02% M_(p) = 293,000 ByIntrinsic Viscosity: M_(y) = 288,800 Toluene @ 30° C. Mv calculated from(h) = 12 × x 10⁻⁵M⁰.71 (h) 0.904 Nominal 4,000 MW Styrene By VaporPressure Osmometer: M_(n) = 3,957 THF, 38 C., four concentrations 08membrane By Size Exclusion Chromatography: M_(w) = 4,136 M_(n) = 3,967M_(p) = 4,000 By Intrinsic Viscosity: Mv = 4,075 THF @ 30° C. Mvcalculated from (h) = 1.71 × 10⁻³M_(v) .712 (h) = 0.06

[0340] Preparation of Dried Nanoscale and Angstrom Scale Particles

[0341] The method of washing residual release coating from the flakeafter it is removed from the drum or carrier is as follows. Using aBuchner Funnel with a 4,000 Ml. capacity and a side outlet for vacuumfiltering and a filter such as a Whatman microfiber filter bothavailable from Fisher Scientific. First add flake to the funnel with thefilter in place and the vacuum on. Wash the flake by rinsing with theappropriate solvent. The solvent used may be Acetone, Ethyl Acetate oran Alcohol depending on the solubility of the release coat. The flakeshould be washed until the residual release coat is removed or reducedto the desired level. The filtered material may then be baked toeliminate volatile materials. This filter cake may also be annealed bybaking at a higher temperature. The spent solvent maybe distilled to bereclaimed and reused. The still bottoms may be reclaimed and reused inthe release coating as mentioned previously. In production, largervacuum filtering devices are available.

[0342] Barrier Materials

[0343] Experiments were run to determine the effect of flake size,pigment-to-binder ratio and coat weight on the moisture vaportransmission rate (MVTR) and oxygen permeability of flake-containingfilms. Large flake size was 20 microns and small flake size was 12microns.

[0344] MVTR test data were as follows: Flake Size P:B Coat Weight (g/m²)MVTR/(g/m²-day) Large 3:1 3.14 4.86 Large 1:1 3.62 5.85 Small 3:1 3.181.82 Small 3:1 0.8 8.86 Large 3:1 0.74 15.0 Large 3:1 3.14 4.86 Large3:1 3.14 4.86 Small 3:1 3.18 1.82 Large 1:1 3.62 5.85 Large 1:1 1.3811.90 Clear Vehicle 1.08 74.4 Dartek SF-502 Nylon Film 58.3

[0345] Further test data revealed an MVTR of 1.2 for small particles, a5:1 pigment-to-binder ratio and a coat weight of 5 gm/m².

[0346] The data show that additions of properly selected flakes can havea dramatic effect on MVTR. For example, the table shows a decrease ofthe MVTR of a nylon film from 75 g/m²-day to 1.8 g/m²-day with the bestconditions being high P:B, small particle size (such as the angstromscale flakes of this invention) and high coat weight. The further testdata shows even better results.

[0347] Based on these data, applications for angstrom scale particles(thickness of less than about 100 angstrom and particles size of lessthan about 20 microns) for example, may include moisture transmissionbarrier materials. In use, the flakes line up in parallel in anessentially common plane and produce barriers to water molecules passingthrough the flake-containing film. Flakes, such as glass flakes, forexample, can be used in polymeric films such as PVC, to inhibitplasticizer migration.

[0348] Electrical Applications

[0349] By running the release-coated carrier at a high rate of speed,deposited metal such as aluminum will produce discrete islands(nano-particles described above). These particles (when removed from therelease layer) can be blended in a flake containing film, or used as-isin a polymeric film. The nano-particle containing film can increaseelectrical capacitance. Capacitance is proportional to dielectricconstant and area and inversely proportioned to the separation distancebetween the capacitor plates. Nano-particles dispersed between largerparticle size flakes raise the dielectric constant and therefore thecapacitance.

[0350] Other uses of nanoparticles are described in Handbook ofDeposition Technologies for Films and Coatings, “Nucleation, FilmGrowth, and Microstructural Evolution,” Joseph Green, Noyes Publication(1994).

1. A process for making angstrom scale flakes comprising: providing avacuum deposition chamber containing a deposition surface; providing arelease coat source and a flake material deposition source in the vacuumdeposition chamber, each directed toward the deposition surface;depositing on the deposition surface under vacuum alternating layers ofa vaporized polymeric release coat layer and a vapor deposited flakelayer from the release coat source and the flake material depositionsource, respectively, to build up in sequence a multi-layer stack offlake material layers separated by and deposited on correspondingintervening release coat layers; the release coat layers comprising athermoplastic polymeric material dissolvable in an organic solvent andwhich, when vaporized under vacuum, forms a smooth continuous barrierlayer and support surface on which each of the flake material layers isformed; the flake material layers comprising a vapor-deposited materialapplied to a film thickness of from about 5 to about 500 Angstroms; andremoving the multi-layer stack from the vacuum chamber and separating itinto flakes by treatment with an organic solvent which dissolves therelease coat layers and yields single layer flakes which are essentiallyfree of the release coat material.
 2. The process according to claim 1in which the release and flake material layers are applied to a chilledrotating drum.
 3. The process according to claim 1 in which the releasecoat material includes a lightly cross-linked polymeric material withweak bond strength or a polymeric material which has been polymerized bychain extension.
 4. The process according to claim 1 in which therelease coat material has a glass transition temperature sufficientlyhigh so that the heat of condensation of the deposited metal layer willnot melt the previously deposited release layer.
 5. The processaccording to claim 1 in which the release coat material is selected fromstyrene or acrylic polymers or blends thereof.
 6. The process accordingto claim 1 in which the layer of flake material comprises a metal layerselected from the group consisting of aluminum, copper, silver,chromium, tin, zinc, indium and nichrome.
 7. The process according toclaim 6 in which the optical density of the vapor deposited metal layeris in the range of about 0.5 to about 2.8 (MacBeth densitometer).
 8. Theprocess according to claim 1 in which the release coat layer has athickness in the range of about 200 to about 400 angstroms.
 9. Theprocess according to claim 1 in which the metal flakes have an aspectratio of 300 or more.
 10. The process according to claim 1 in which theflake material comprises an inorganic material.
 11. A process for makingangstrom scale metal flakes comprising: providing a vacuum depositionchamber containing a deposition surface; providing a release coat sourceand a metal deposition source in the vacuum deposition chamber, eachdirected toward the deposition surface; depositing on the depositionsurface under vacuum alternating layers of a vaporized polymeric releasecoat layer and a vapor deposited metal layer from the release coatsource and the metal deposition source, respectively, to build up insequence a multi-layer stack of metal layers separated by and depositedon corresponding intervening release coat layers; the release coatlayers comprising a thermoplastic polymeric material which isdissolvable in an organic solvent and which, when vaporized undervacuum, forms a smooth continuous barrier layer and support surface onwhich each of the reflective metal layers is formed; the reflectivemetal layers comprising vapor-deposited aluminum in elemental formapplied to a film thickness from about 5 to about 500 Angstroms; andremoving the multi-layer stack from the vacuum chamber and separating itinto metal flakes by treatment with an organic solvent which dissolvesthe release coat layers and yields single layer flakes having surfacesessentially free of the release coat material.
 12. The process accordingto claim 10 in which the release coat material comprises polystyrene oracrylic resin or blends thereof.
 13. A process for making angstrom scalemulti-layer reflective metal flakes with protective outer coatingscomprising: providing a vacuum deposition chamber containing adeposition surface; providing a release coat vapor deposition source, ametal vapor deposition source and a protective coating vapor depositionsource in the vacuum deposition chamber, each directed toward thedeposition surface; vapor depositing on the deposition surface undervacuum, in the following sequence, (1) a layer of release coat materialfrom the release coat vapor deposition source, (2) a first protectiveouter coating from the protective coating vapor deposition source, (3) areflective metal layer from the metal vapor deposition source, (4) asecond protective coating from the protective outer coating vapordeposition source, and (5) a further layer of a release coat materialfrom the release coat vapor deposition source, to build-up in sequence astack of multi-layer flake material comprising metal layers each bondedto first and second protective outer coatings with intervening releasecoat layers between adjacent layers of multi-layer flake material; therelease coat layers comprising thermoplastic polymeric material which isdissolvable in an organic solvent and which, when vaporized undervacuum, forms a smooth continuous barrier layer and support surface onwhich each layer of multi-layer flake material is formed; the reflectivemetal layers comprising vapor-deposited metal in elemental form appliedto a film thickness from about 10 to about 2000 Angstroms; and removingthe stacks of multi-layer flake material from the vacuum chamber andseparating them into flakes by treatment with an organic solvent whichdissolves the release coat layers and yields multi-layer flakescomprising metal layers bonded on opposite sides to the first and secondprotective outer layers, the flakes having their surfaces essentiallyfree of the release coat material.
 14. The process according to claim 13in which the protective outer coating comprises a transparent polymericmaterial applied from its corresponding vapor deposition source andcured in the vacuum chamber to a thermoset condition.
 15. The processaccording to claim 13 in which the protective outer coating comprises avapor deposited inorganic material selected from the group consisting ofmagnesium fluoride, silicon monoxide, silicon dioxide, aluminum oxide,aluminum fluoride, indium tin oxide, titanium dioxide, and zinc sulfide.16. The process according to claim 13 in which the multi-layer flakesare selected from the group consisting of inorganic/metal oralloy/inorganic, metal/inorganic/metal, and crop-linked polymer outerlayers on metal or alloy.
 17. A process for making angstrom scale flakescomprising: providing a vacuum deposition chamber containing adeposition surface; providing a release coat source and an inorganicflake material deposition source in the vacuum deposition chamber, eachdirected toward the deposition surface; depositing on the depositionsurface under vacuum alternating layers of a vaporized polymeric releasecoat layer and a vapor deposited inorganic flake material from therelease coat source and the flake material deposition source,respectively, to build up in sequence a multi-layer stack of inorganicflake material separated by and deposited on corresponding interveningrelease coat layers; the release coat layers comprising a thermoplasticpolymeric material dissolvable in an organic solvent and which, whenvaporized under vacuum, forms a smooth continuous barrier layer andsupport surface on which each of the inorganic flake material layers isformed; the inorganic flake material layers comprising a vapor-depositedinorganic material having a thickness in the range of about 5 to about500 angstroms, and in which the inorganic material is selected from thegroup consisting of magnesium fluoride, silicon monoxide, silicondioxide, aluminum oxide, aluminum fluoride, indium tin oxide, titaniumdioxide and zinc sulfide; and removing the multi-layer stack from thevacuum chamber and separating it into flakes of inorganic material bytreatment with an organic solvent which dissolves the release coatlayers and yields single layer flakes of inorganic material essentiallyfree of the release coat material.
 18. A process for making angstromscale particles, comprising: providing a vacuum deposition chambercontaining a deposition surface; providing a release coat depositionsource and a particle deposition source in the vacuum depositionchamber; depositing on the deposition surface a vaporized polymericrelease coat layer from the release coat deposition source, the releasecoat layer comprising a thermoplastic polymeric material dissolvable inan organic solvent and which, when vaporized under vacuum, forms asmooth continuous support surface on which a layer of particle materialcan be vapor deposited; vapor depositing on the release coat surface adiscontinuous layer of particle material to form discrete islands ofangstrom scale particle material; and removing the particle material bytreating it and the release coat layer with organic solvent to dissolvethe release coat material and produce discrete angstrom scale particlesessentially free of release coat material.